EP3118256B1 - Zusammensetzung mit ptfe als hauptkomponente, gemischtes pulver und material zum formen - Google Patents

Zusammensetzung mit ptfe als hauptkomponente, gemischtes pulver und material zum formen Download PDF

Info

Publication number
EP3118256B1
EP3118256B1 EP16172614.6A EP16172614A EP3118256B1 EP 3118256 B1 EP3118256 B1 EP 3118256B1 EP 16172614 A EP16172614 A EP 16172614A EP 3118256 B1 EP3118256 B1 EP 3118256B1
Authority
EP
European Patent Office
Prior art keywords
filtering medium
porous membrane
ptfe
fibrillated
component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP16172614.6A
Other languages
English (en)
French (fr)
Other versions
EP3118256A1 (de
Inventor
Shinichi Chaen
Hideyuki Kiyotani
Kunihiko Inui
Taku Yamanaka
Li Bao
Yoshiyuki Shibuya
Seigo Yamamoto
Makoto Kobayashi
Shunji Kasai
Hitoshi Niinuma
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daikin Industries Ltd
Original Assignee
Daikin Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daikin Industries Ltd filed Critical Daikin Industries Ltd
Publication of EP3118256A1 publication Critical patent/EP3118256A1/de
Application granted granted Critical
Publication of EP3118256B1 publication Critical patent/EP3118256B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/54—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms
    • B01D46/543—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms using membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/0001—Making filtering elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/56—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with multiple filtering elements, characterised by their mutual disposition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/36—Polytetrafluoroethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D99/00—Subject matter not provided for in other groups of this subclass
    • B29D99/005—Producing membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
    • B29K2027/18—PTFE, i.e. polytetrafluorethene, e.g. ePTFE, i.e. expanded polytetrafluorethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the present invention relates to a composition having PTFE as a main component, mixed powder, a material for molding, a filtering medium for filter, an air filter unit, and a method for manufacturing a porous membrane.
  • a porous membrane composed of polytetrafluoroethylene (PTFE) (hereinbelow, also referred to as a "porous PTFE membrane”) is used as a filter for collecting fine particles.
  • PTFE membrane is particularly preferably used for a HEPA filter (High Efficiency Particulate Air Filter) or a ULPA filter (Ultra low Penetration Air Filter).
  • a filtering medium composed of glass fiber has been conventionally used. However, there is a problem that it has a high pressure loss. Meanwhile, a filter with a low pressure, which is achieved by applying the porous PTFE membrane to a filtering medium, has been also conventionally commercialized. However, there is a problem that, since a pressure loss easily increases due to an occurrence of surface filtration as caused by a dense structure of the porous PTFE membrane, the life span is equal to or less than half of a glass fiber filter.
  • a filtering medium adhered with an MB (Melt Blown) non-woven fabric at upstream side of the porous PTFE membrane is also suggested.
  • the filtering medium thickness increases according to adhesion of MB non-woven fabric, and thus there is a problem that an area to which the folded filtering medium is inserted while it is incorporated into an air filter unit is reduced and also the price of the filtering medium increases.
  • porous PTFE membrane of a related art it is known that high air permeability is obtained by adding PTFE that is not fibrillated by drawing to PTFE that is fibrillated by drawing during manufacture (for example, see Patent Literatures 1 and 2).
  • This porous PTFE membrane has fibrils and knotted portions that are connected to each other by fibrils.
  • the membrane structure changes as compressive force or the like is applied during a post step like laminating an air permeable support, and thus the filter performance such as a pressure loss, PF value, or filter life span may be deteriorated.
  • the PTFE molded article of a related art is easily affected by external force after being processed into a porous membrane.
  • the influence is significant for a use in which a molded article with low filling rate (for example, 1 to 20%) is used.
  • a molded article with low filling rate for example, 1 to 20%
  • desired performances may be exhibited right after processing into a porous body (for example, the aforementioned porous membrane, a sheet used for a cushion material, packing, or the like)
  • the structure with low filling rate is impaired due to external force applied thereto by post processing or the like, and thus there are many cases in which the performances of the molded article are deteriorated.
  • a purpose of the present invention is to provide a composition with which a molded article, which is difficult to be deformed by external force even at low filling rate, can be obtained, mixed powder, and a material for molding.
  • Inventors of the present invention conducted intensive studies to solve the aforementioned problems. As a result, they found that, when a composition having a hot melt processable component that is not fibrillated in addition to PTFE that is fibrillated by drawing and a non-hot melt processable component that is not fibrillated such as low molecular weight PTFE that is fibrillated is used and a porous membrane is prepared with it and applied to an air filter, for example, the structure of the porous PTFE membrane can be improved, and both of a low pressure loss and long life span can be satisfied. It is also found that, as the strength of the knotted portions is increased, a decrease in filter performance is suppressed even when compressive force or the like is applied during a post process like lamination of an air permeable support.
  • the present invention provides a composition containing polytetrafluoroethylene that can be fibrillated, a non-hot melt processable component that is not fibrillated, and a hot melt processable component with a melting point of lower than 320°C that is not fibrillated, as defined in claim 1 and a material for molding as defined in claim 2.
  • the present invention also provides a porous membrane used as a filtering medium for a filter to capture fine particles in fluid, in which the porous membrane contains fibrils including polytetrafluoroethylene that can be fibrillated, and knotted portions containing polytetrafluoroethylene that can be fibrillated, and the knotted portions further contain a non-hot melt processable component that is not fibrillated and also a hot melt processable component with a melting point of lower than 320°C that is not fibrillated, as defined in claims 1 or 2, and the use of the material of claim 2 for molding a porous membrane.
  • the porous membrane contains fibrils including polytetrafluoroethylene that can be fibrillated, and knotted portions containing polytetrafluoroethylene that can be fibrillated, and the knotted portions further contain a non-hot melt processable component that is not fibrillated and also a hot melt processable component with a melting point of lower than 320°C that is not fibrillated, as defined in claims 1 or 2, and the use
  • the inventors of the present invention also found that the filtering medium for an air filter described below has high dust holding capacity while having significantly improved collecting performance.
  • a method for manufacturing a porous membrane used for a filtering medium for a filter to capture fine particles in fluid includes:
  • the obtained porous membrane is unlikely to have deformation caused by external force even when the filling ratio of a molded article is low.
  • the produced porous membrane has low filling ratio but high air permeability, not only a filtering medium with a low pressure loss can be obtained by using it, but as the low density structure is maintained, the filter life span is also significantly improved so that the life span like a glass fiber filter can be achieved. Further, as the decrease in filter performance is suppressed even when compressive force or the like is applied in a post step like lamination of an air permeable support, fewer problems are caused during the manufacture.
  • a decrease in the collecting performance is suppressed even with high dust holding capacity, and therefore a filtering medium for an air filter and an air filter unit which does not generate impurities are obtained. Further, according to the manufacturing method of the present invention, a porous membrane used for a filtering medium for an air filter is obtained.
  • the mixed powder, the material for molding and the porous membrane, according to the invention are described.
  • the composition is described in conjunction with the description of method for manufacturing a porous membrane.
  • Fig. 1 is a schematic drawing illustrating the porous membrane.
  • Fig. 2 is a drawing describing the structure of the porous membrane.
  • the porous membrane 1 is used for a filtering medium to capture dust in fluid, and it has the fibril 3 and the knotted portion 5 that is connected to each other via the fibril 3.
  • the fibril 3 includes polytetrafluoroethylene that can be fibrillated.
  • the polytetrafluoroethylene that can be fibrillated is high molecular weight PTFE which is obtained by emulsion polymerization or suspension polymerization of tetrafluoroethylene (TFE), for example.
  • TFE tetrafluoroethylene
  • the high molecular weight means that fibrillation can be easily achieved during manufacture of a porous membrane so that a fibril with long fiber length is obtained and, as having standard specific gravity (SSG) of 2.130 to 2.230, and substantially exhibiting no melt fluidization due to high melt viscosity.
  • SSG standard specific gravity
  • SSG of PTFE that can be fibrillated is preferably 2.130 to 2.190, and more preferably 2.140 to 2.170.
  • SSG is excessively high, the drawing property of the mixture of the non-hot melt processable component that is not fibrillated and the hot melt processable component that is not fibrillated described below may be deteriorated.
  • SSG is excessively low, the rolling property is deteriorated so that the homogeneity of the porous membrane may be deteriorated and the pressure loss of the porous membrane may increase.
  • PTFE obtained by emulsion polymerization is preferable.
  • the standard specific gravity (SSG) is measured on the basis of ASTM D 4895.
  • the presence or absence of fibrillating property that is, the possibility of having fibrillation, can be determined based on the possibility of having paste extrusion, which is the representative method for molding high molecular weight PTFE powder made of TFE polymer, generally, paste extrusion is possible since high molecular weight PTFE has a fibrillating property.
  • paste extrusion which is the representative method for molding high molecular weight PTFE powder made of TFE polymer, generally, paste extrusion is possible since high molecular weight PTFE has a fibrillating property.
  • the high molecular weight PTFE can be modified polytetrafluoroethylene (hereinbelow, referred to as the modified PTFE), homo polytetrafluoroethylene (hereinbelow, referred to as the homo PTFE), or a mixture of the modified PTFE and the homo PTFE.
  • modified PTFE polytetrafluoroethylene
  • homo polytetrafluoroethylene hereinbelow, referred to as the homo PTFE
  • a mixture of the modified PTFE and the homo PTFE a mixture of the modified PTFE and the homo PTFE.
  • the homo PTFE is not particularly limited, and any homo PTFE can be preferably used if it is described in JP 53-60979 A , JP 57-135 A , JP 61-16907 A , JP 62-104816 A , JP 62-190206 A , JP 63-137906 A , JP 2000-143727 A , JP 2002-201217 A , WO 2007/046345 A , WO 2007/119829 A , WO 2009/001894 A , WO 2010/113950 A , or WO 2013/027850 A .
  • the homo PTFE having high drawing characteristics disclosed in JP 57-135 A , JP 63-137906 A , JP 2000-143727 A , JP 2002-201217 A , WO 2007/046345 A , WO 2007/119829 A , or WO 2010/113950 A is preferable.
  • the modified PTFE includes TFE and a monomer other than TFE (hereinbelow, referred to as a modified monomer).
  • the modified monomer is generally those modified homogeneously with a modified monomer, those modified at early stage of a polymerization reaction, or those modified at final stage of a polymerization reaction, but it is not particularly limited.
  • any modified PTFE can be preferably used if it is described in JP 60-42446 A , JP 61-16907 A , JP 62-104816 A , JP 62-190206 A , JP 64-1711 A , JP 2-261810 A , JP 11-240917 A , JP 11-240918 A , WO 2003/033555 A , WO 2005/061567 A , WO 2007/005361 A , WO 2011/055824 A , or WO 2013/027850 A for example.
  • the modified PTFE having high drawing characteristics disclosed in JP 61-16907 A , JP 62-104816 A , JP 64-1711 A , JP 11-240917 A , WO 2003/033555 A , WO 2005/061567 A , WO 2007/005361 A , or WO 2011/055824 A is preferable.
  • the modified PTFE contains a TFE unit based on TFE and a modified monomer unit based on the modified monomer.
  • the modified PTFE is preferably contained at 0.001 to 0.500% by weight, and more preferably at 0.01 to 0.30% by weight of the entire monomer units.
  • the modified monomer unit is a part of the molecular structure of the modified PTFE and it is a part derived from the modified monomer.
  • the entire monomer units are a part derived from every monomer in the molecular structure of the modified PTFE.
  • the modified monomer is not particularly limited, if it is copolymerizable with TFE.
  • examples thereof include perfluoro-olefin such as hexafluoropropylene (HFP); chlorofluoro-olefin such as chlorotrifluoroethylene (CTFE); hydrogen-containing fluoro-olefin such as trifluoroethylene or vinylidene fluoride (VDF); perfluorovinyl ether; perfluoroalkyl ethylene (PFAE) and ethylene or the like.
  • the modified monomer which is used may be either one type or plural types.
  • Rf represents a perfluoro organic group.
  • the perfluoro organic group is an organic group in which every hydrogen atom bound to the carbon atom is substituted with a fluorine atom.
  • the perfluoro organic group may have ether oxygen.
  • perfluorovinyl ether examples include perfluoro(alkyl vinyl ether) (PAVE) of the general formula (1) in which Rf is a perfluoroalkyl group having 1 to 10 carbon atoms. Carbon atom number of the perfluoroalkyl group is preferably 1 to 5.
  • Rf is a perfluoroalkyl group having 1 to 10 carbon atoms. Carbon atom number of the perfluoroalkyl group is preferably 1 to 5.
  • the perfluoroalkyl group in PAVE include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group for example.
  • Preferred examples of PAVE include perfluoropropyl vinyl ether (PPVE) and perfluoromethyl vinyl ether (PMVE).
  • Perfluoroalkyl ethylene is not particularly limited, and examples thereof include perfluorobutyl ethylene (PFBE) and perfluorohexyl ethylene (PFHE) for example.
  • the modified monomer of the modified PTFE at least one selected from a group consisting HFP, CTFE, VDF, PAVE, PFAE, and ethylene is preferable.
  • the homo PTFE is contained in an amount of more than 50% by weight of the PTFE that can be fibrillated.
  • the PTFE that can be fibrillated is, from the viewpoint of maintaining the fiber structure of the porous membrane 1, preferably contained in an amount of more than 50% by weight of the porous membrane 1.
  • the knotted portion 5 is a part that is connected to each other via the fibril 3, and it contains PTFE that can be fibrillated, the non-hot melt processable component that is not fibrillated, and the hot melt processable component with a melting point of lower than 320°C that is not fibrillated.
  • the resulting knotted portion 5 is formed to have relatively large size in the porous membrane 1, and accordingly the porous membrane 1 having higher thickness than that of a related art is formed. Further, as containing a hot melt processable component that is not fibrillated, the resulting knotted portion 5 is relatively hard and plays a role of a column which supports the porous membrane 1 in thickness direction.
  • the PTFE that can be fibrillated, which is contained in the knotted portion 5, is the same as the PTFE that can be fibrillated, which is used in the fibril 3 described above.
  • the non-hot melt processable component that is not fibrillated is mainly localized in the knotted portion 5 as non-fibrous particles and it functions to suppress the fibrillation of PTFE that can be fibrillated.
  • the non-hot melt processable component that is not fibrillated includes low molecular weight PTFE, a thermosetting resin, and an inorganic filler.
  • the low molecular weight PTFE has high melt viscosity, it can stay in the knotted portions even when it is processed at a temperature which is higher than the melting point.
  • the low molecular weight PTFE means PTFE with number average molecular weight of 600,000 or less, melting point of between 320 to 335°C, and melt viscosity at 380°C of 100 to 7.0 ⁇ 10 5 Pa ⁇ s (see, JP 10-147617 A ).
  • the method for producing low molecular weight PTFE a thermal decomposition method in which high molecular weight PTFE powder (molding powder) obtained from suspension polymerization of TFE or high molecular weight PTFE powder (fine powder) obtained from emulsion polymerization of TFE and a specific fluorinated compound are reacted according to contact at high temperature (see, JP 61-162503 A ), a method of illuminating ionizing radiation to high molecular weight PTFE powder or a molded article (see, JP 48-78252 A ), and a method of polymerizing directly TFE with a chain transfer agent (see, WO 2004/050727 A , WO 2009/020187 A , and WO 2010/114033 A ) are known.
  • the low molecular weight PTFE can be also the homo PTFE or the modified PTFE including a modified monomer described above.
  • the low molecular weight PTFE has no fibrillating property.
  • the presence or absence of the fibrillating property can be determined by the aforementioned method.
  • the unsintered molded article obtained by paste extrusion has substantially no strength or elongation, for example, elongation of 0%, and it breaks when pulled.
  • the low molecular weight PTFE used in the present invention is not particularly limited. However, those having melt viscosity at 380°C of 1000 Pa ⁇ s or more are preferable. Those having melt viscosity at 380°C of 5000 Pa ⁇ s or more are more preferable. Those having melt viscosity at 380°C of 10000 Pa ⁇ s or more are even more preferable. As described above, when the melt viscosity is high, the non-hot melt processable component that is not fibrillated can stay in the knotted portion 5 even when a hot melt processable component that is not fibrillated is melt during manufacture of a porous membrane so that the fibrillation can be suppressed.
  • thermosetting resin examples include each resin of epoxy, silicone, polyester, polyurethane, polyimide, and phenol, like, for example. From the viewpoint of the workability of the co-coagulation, a resin dispersed in water in a non-cured state is preferably used as the thermosetting resin. All of those thermosetting resins can be obtained as a commercially available product.
  • the inorganic filler As for the inorganic filler, talc, mica, calcium silicate, glass fiber, calcium carbonate, magnesium carbonate, carbon fiber, barium sulfate, calcium sulfate, or the like are used. Among them, from the viewpoint of affinity with PTFE and specific gravity, talc is preferably used. From the viewpoint for forming stably dispersion during manufacture of the porous membrane 1, those having particle diameter of 3 to 20 ⁇ m are preferably used. All of those inorganic fillers can be obtained as a commercially available product.
  • the non-hot melt processable component that is not fibrillated is contained at 20 to 40% by weight, and more preferably at 30% by weight. By containing it at 20 to 40% by weight, fibrillation of PTFE that can be fibrillated can be more effectively suppressed.
  • the hot melt processable component with a melting point of lower than 320°C that is not fibrillated (hereinbelow, also referred to as the hot melt processable component that is not fibrillated) has fluidity at melting so that it melts during the manufacture (drawing) of the porous membrane 1 and can be hardened in the knotted portion 5, thus increasing the strength of the entire porous membrane 1. Accordingly, deterioration in filter performance can be suppressed when it is compressed during a post step.
  • the hot melt processable component that is not fibrillated preferably exhibits the melt viscosity of less than 10000 Pa ⁇ s at 380°C.
  • the melting point of the hot melt processable component that is not fibrillated is obtained from a peak top in a diagram of latent heat of fusion, which is obtained by, by using differential scanning calorimetry (DSC), once complete melting by increasing the temperature at temperature increase rate of 10°C/minute to melting temperature or higher, cooling at 10°C/minute to melting temperature or lower, and increasing the temperature again at 10°C/minute.
  • DSC differential scanning calorimetry
  • the hot melt processable component that is not fibrillated includes a hot melt processable fluoro polymer, silicone, polystyrene, polyethylene terephthalate (PET), polyester, polyamide, acrylic resin, urethane resin, or a mixture thereof, and those capable of fully exhibiting melting property and fluidity at the drawing temperature for manufacturing the porous membrane 1 can be included.
  • a hot melt processable fluoro polymer is preferable.
  • R each independently is selected from H, F, Cl, alkyl having 1 to 8 carbon atoms, aryl having 6 to 8 carbon atoms, cyclic alkyl having 3 to 10 carbon atoms, and perfluoroalkyl having 1 to 8 carbon atoms, and
  • Useful examples of the compound represented by the general formula (2) include, although not limited thereto, perfluoroolefin such as fluoroethylene, VDF, trifluoroethylene, TFE, or HFP, chlorofluoroolefin such as CTFE or dichlorodifluoroethylene, (perfluoroalkyl)ethylene such as PFBE or PFHE, perfluoro-1,3-dioxol, and a mixture thereof.
  • perfluoroolefin such as fluoroethylene, VDF, trifluoroethylene, TFE, or HFP
  • chlorofluoroolefin such as CTFE or dichlorodifluoroethylene
  • (perfluoroalkyl)ethylene such as PFBE or PFHE
  • perfluoro-1,3-dioxol and a mixture thereof.
  • the fluoropolymer contains a copolymer that is derived from copolymerization between at least one monomer represented by the above general formula (2) and at least one copolymerizable comonomer represented by the above general formula (1) and/or following general formula (3)
  • R 2 C CR 2 ⁇ (3)
  • Useful examples of the compound represented by the general formula (1) include PAVE and preferred examples include PPVE and PMVE.
  • Useful examples of the compound represented by the general formula (3) include ethylene and propylene.
  • fluoro polymer More specific examples of the fluoro polymer include polyfluoroethylene derived from polymerization of fluoroethylene, polyvinyldiene fluoride (PVDF) derived from polymerization of VDF, polychlorotrifluoroethylene (PCTFE) derived from polymerization of CTFE, a fluoro polymer derived from copolymerization of two or more different monomers represented by the above general formula (2), and a fluoro polymer derived from copolymerization between at least one monomer of the above general formula (2) and at least one monomer represented by the above general formula (1) and/or at least one monomer represented by the above general formula (3).
  • PVDF polyvinyldiene fluoride
  • PCTFE polychlorotrifluoroethylene
  • polymer examples include a polymer having a copolymer unit derived from VDF and HFP and a polymer derived from TFE and at least one copolymerizable comonomer (at least 3% by weight) other than TFE.
  • fluoro polymer examples include TFE/PAVE copolymer (PFA), TFE/PAVE/CTFE copolymer, TFE/HFP copolymer (FEP), TFE/ethylene copolymer (ETFE), TFE/HFP/ethylene copolymer (EFEP), TFE/VDF copolymer, TFE/VDF/HFP copolymer, TFE/VDF/CTFE copolymer and a mixture thereof.
  • Content of the hot melt processable component that is not fibrillated in the porous membrane 1 is equal to or more than 0.1 by weight but less than 20% by weight.
  • the hot melt processable component that is not fibrillated is dispersed in an area other than the knotted portion 5 of the porous membrane 1 so that the pressure loss becomes high when it is used for a filtering medium for an air filter described below, in particular. Further, because it is difficult to perform drawing at high ratio like elongation area ratio of 40 times or more described below, a problem is caused in manufacturing the porous membrane 1.
  • Content of the hot melt processable component that is not fibrillated in the porous membrane 1 is preferably 15% by weight or less, and more preferably 10% by weight or less. Further, content of the hot melt processable component that is not fibrillated in the porous membrane 1 is, from the viewpoint of ensuring the strength of the porous membrane 1, preferably 0.5% by weight or more. It is particularly preferably 5% by weight or so.
  • the content of the hot melt processable component that is not fibrillated is preferably 10% by weight or less to have good drawing with elongation area ratio of 40 to 800 times.
  • the porous membrane 1 preferably has the filling ratio of 1 to 20%, and more preferably 2 to 10%, in which the filling ratio is obtained by the following equation.
  • Filling ratio % 1 ⁇ Pore volume in porous membrane / Volume of porous membrane ⁇ 100
  • the porous membrane 1 with above filling ratio has membrane thickness reduction rate of 1.5 ⁇ m/sec or less, which is described below when pressure of 6.4 kPa is applied.
  • the porous membrane 1 can be obtained by the method for manufacturing a porous membrane which is described below. Further, the porous membrane 1 can be manufactured by using the composition, mixed powder, and material for molding that are described below, for example.
  • the porous membrane 1 can be used for a filtering medium for an air filter or a liquid filter.
  • the porous membrane 1 is preferably used for a filtering medium for an air filter, and the film thickness is 150 ⁇ m or less, and preferably 7 to 120 ⁇ m. Further, the average fiber diameter of the fiber constituting the porous membrane 1 is 50 nm to 200 nm, and preferably 80 nm to 200 nm.
  • Fig. 3 is a drawing illustrating the filtering medium 9.
  • the filtering medium 9 is to capture dust in gas, and it includes the aforementioned porous membrane 1 and the air permeable support 13 laminated on both sides of the porous membrane 1.
  • the material and structure of the air permeable support layer 13 are not particularly limited, a non-woven fabric, a woven fabric, a metal mesh, a resin net, or the like are used, for example. Among them, a non-woven fabric having strength, collecting property, flexibility, and heat fusion property in terms of workability is preferable.
  • the non-woven fabric can be a non-woven fabric in which part or all constituting fibers have a core/sheath structure or a bilayer non-woven fabric including two layers having a material with low melting point and a material with high melting point.
  • Material of the non-woven fabric is not particularly limited, and polyolefin (PE, PP, or the like), polyamide, polyester (PET or the like), aromatic polyamide, or a composite material of them can be used.
  • the core component preferably has higher melting point than the sheath component. Examples of the combination of each material of the core/sheath include PET/PE and polyester with high melting point/polyester with low melting point.
  • the air permeable support 13 can be adhered to the porous membrane 1 by partial melting of the air permeable support 13 by heating, by melting of a hot melt resin, by using an anchor effect, or by using the adhesion with reactive adhesives or the like.
  • Weight and thickness of the air permeable support 13 per unit area are not particularly limited, and they can be the same or different on two sides of the porous membrane 1.
  • the porous membrane can be a single layer or a multilayer in which plural pieces are overlaid.
  • the plural porous membranes can be the same type, or the air permeable support 13 can be inserted between them.
  • the air permeable support 13 can be laminated on just one side of the porous membrane 1 in other embodiment.
  • the filtering medium 9 can have a pre-collecting layer (not illustrated) further laminated on the air permeable support 13 on a single side (in general, at upstream side of air flow which passes through the filtering medium).
  • a pre-collecting layer those obtained by a melt blown method are used, for example.
  • the material of the pre-collecting layer include, in addition to polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyamide (PA), polyacrylonitrile (PAN), polyvinylidene fluoride (PVdF), polyvinyl alcohol (PVA), and polyurethane (PU) or the like.
  • the pre-collecting layer can be adhered to the porous membrane 1 by thermal lamination using a hot melt resin, for example.
  • the filtering medium 9 provided with the pre-collecting layer is preferably used as a HEPA filter. In that case, the air permeable support 13 with different thickness but the same weight per unit area at two sides of the porous membrane is used. Meanwhile, when the filtering medium is used as a ULPA filter, the aforementioned pre-collecting layer is unnecessary. Further, the filtering medium 9 can have a pre-collecting layer directly laminated on the porous membrane 1 instead of the air permeable support 13.
  • the knotted portion 5 is hardened by a hot melt processable component that is not fibrillated as described above, and thus the strength of the porous membrane 1 is enhanced. For such reasons, even when compressive force or the like is applied at the time of laminating the air permeable support 13 on the porous membrane 1, a deterioration of filter performance like pressure loss, PF value, and filter life span as caused by squashing of the membrane structure of the porous membrane 1 is suppressed.
  • the porous membrane 1 used for the filtering medium 9 mainly includes PTFE that can be fibrillated, a porous membrane with low filling ratio and high air permeability can be obtained.
  • a porous membrane with low filling ratio and high air permeability can be obtained.
  • the low filling ratio means the filling ratio of 1 to 20%, which is calculated by the aforementioned equation.
  • the high air permeability means a low pressure loss.
  • the low pressure loss indicates that the pressure loss measured by the following method is less than 200 Pa.
  • the filter life span is measured by the method described below.
  • the filtering medium 9 is used for the following use, for example.
  • a field of ULPA filter for manufacturing a semiconductor
  • HEPA filter for hospital use or manufacturing a semiconductor
  • a columnar cartridge filter for industrial use
  • a bag filter for industrial use
  • a heat resistant bag filer for exhaust fumes treatment
  • a heat resistant pleats filter for exhaust fumes treatment
  • SINBRAN registered trademark
  • filter for industrial use
  • a catalyst filter for exhaust fuems treatment
  • a filter having adsorbent for HDD's (Hard Disk Drive's) build-in
  • a bent filter having adsorbent for HDD's build-in
  • a bent filter for HDD's build-in
  • a bent filter for HDD's build-in
  • a filter for vacuum cleaner for use in a vacuum cleaner
  • universal multilayer felt medium for a cartridge filter for GT (Gire-Tournois) (for use in GT compatible product), and a cooling filter (for use in casing of electronic device), and the like
  • GT Greenwich Mean Time Warner Inc.
  • a field of ventilation or inner pressure adjustment such as a material for freeze drying like a container for freeze drying, a ventilation material for an electronic circuit or a lamp of an automobile, a use for container such as cap of a container, a use for protection and a ventilation of an electronic device, and a use for ventilation in medical use;
  • a field of liquid filtration such as a filter for filtering semiconductor liquid (for manufacturing a semiconductor), a hydrophilic PTFE filter (for manufacturing a semiconductor), a filter for chemical reagent (for treating chemical liquid), a filter for pure water manufacturing line (for manufacturing pure water), and a filter for reverse washing type liquid filtration (for treating industrial waste water).
  • Fig. 4 is a perspective view illustrating the air filter unit 20.
  • the air filter unit 20 includes the processed filtering medium 21, the separator 22, and the frame body 24.
  • the processed filtering medium 21 is a filtering medium with a zigzag shape, which is obtained by pleats processing of the filtering medium 9 in sheet shape by performing outward folding and inward folding to have a peak part and a valley part.
  • the separator 22 is to maintain the zigzag shape of the processed filtering medium 21, and due to corrugation processing of a thin plate, it has a wave shape and is inserted to the valley part.
  • the frame body 24 is formed by combining panels, and the processed filtering medium 21 inserted with the separator 22 is installed inside while keeping the entire separator 22. Meanwhile, in Fig. 4 , the processed filtering medium 21, the separator 22, and the frame body 24 are illustrated in partially cut-out state.
  • the strength of the porous membrane used for the processed filtering medium 21 is improved in the air filter unit as described above, even when compressive force or the like is applied during processing of a filtering medium into a zigzag shape, a deterioration of the filter performance such as pressure loss, PF value, or filter life span as caused by squashing of the membrane structure of the porous membrane is suppressed. Further, even though the pressure loss is lower than an air filter unit of a related art in which a filtering medium of glass fiber is used, the filter life span equivalent thereto is obtained.
  • the air filter unit can be manufactured as an air filter unit of mini pleats type illustrated in Fig. 3 of JP 2012-020274 A , for example, by using the filtering medium described above.
  • the method for manufacturing a porous membrane includes:
  • the three components can be mixed by other method instead of performing the co-coagulation of aqueous dispersions of the three components in the step a). From the viewpoint of homogeneous mixing of the three components, mixing the three components by the co-coagulation as described above is preferable.
  • the mixed powder, material for molding all contain the component A, the component B, and the component C, and the component C is contained at being equal to or greater than 0.1 % but less than 20% by weight.
  • Each of the component A, the component B, and the component C is the same as the PTFE that can be fibrillated, the non-hot melt processable component that is not fibrillated, and the hot melt processable component that is not fibrillated that are described above, respectively.
  • the material for molding is, for example, a material for molding a porous membrane which is used for a filtering medium for a filter to capture fine particles in fluid.
  • the fine powder obtained by co-coagulation that is used in the following example, powder obtained by mixing two kinds of the three materials by co-coagulation and mixing the remaining one kind of the component by using a mixer, and powder obtained by mixing three materials by using a mixer can be mentioned.
  • the material for molding indicates those obtained after adjustment for processing to mold the composition and examples thereof include those added with a processing aid those with adjusted particle size, and those obtained after preliminary molding.
  • the material for molding may include, in addition to the aforementioned three components and the processing aid, a well-known additive.
  • the well-known additive include a carbon material such as carbon nanotube or carbon black, a pigment, a photocatalyst, activated carbon, an anti-microbial agent, an adsorbent, and a deodorant.
  • the composition of the present invention can be manufactured by various methods.
  • the composition when the composition is mixed powder, it can be manufactured by a method in which powder of the component A, powder of the component B, and powder of the component C are mixed by a common mixer, a method in which co-coagulated powder is obtained by co-coagulating (that is, the step a) described above) three aqueous dispersions each containing the component A, the component B, and the component C, or a method of mixing mixed powder which is obtained by co-coagulating in advance an aqueous dispersion containing any two components of the component A, the component B, and the component C with powder of the remaining one component using a common mixer.
  • the composition of the present invention is preferably obtained by co-coagulating three aqueous dispersions each containing the component A, the component B, and the component C.
  • the size of the mixed powder obtained by co-coagulation is not particularly limited, but the average particle diameter is 100 to 1000 ⁇ m, for example. Preferably, it is 300 to 800 ⁇ m. In that case, the average particle diameter is measured on the basis of JIS K6891.
  • the apparent density of the mixed powder that is obtained by co-coagulation is not particularly limited. However, it is preferably 0.40 to 0.60 g/ml, and more preferably 0.45 to 0.55 g/ml. The apparent density is measured on the basis of JIS K6892.
  • the molded article obtained by molding with use of the composition, mixed powder, and material for molding of the present invention is also used, in addition to desirable use in a field of various filters, a field of ventilation/adjustment of inner pressure, or liquid filtration filter in the following fields, for example.
  • An electrochemical field such as dielectric prepreg, a material for shielding EMI (Electro Magnetic Interference), and a heat transfer material, more specifically, a printed wire board, a shielding material for blocking electrons, a heat transfer material for electric insulation, a material for electric insulation, an electrolytic device such as saline, or a reinforce material of a conductive polymer membrane used for a battery;
  • a field of air filter sealing medium such as gasket, packing, pump diaphragm, pump tube, and sealing material for an airplane;
  • a field of common consumer goods such as clothing (clothing for everyday life), cable guide (operation wire for a bike), clothing for a bike (clothing for everyday life), a cast liner (medical supporter), filter for vacuum cleaner, bag pipe (musical instrument), cable (signal cable or the like for guitar), or string (for string instrument);
  • a field of fibers such as PTFE fiber (fiber material), thread for sewing machine (textile), weaving yarn (textile), or rope: and
  • a medical field
  • examples of the co-coagulation include the followings:
  • the method of (i) above is preferable.
  • the coagulation is preferably performed by adding any one of an acid such as nitric acid, hydrochloric acid, or sulfuric acid; a metal salt such as magnesium chloride, calcium chloride, sodium chloride, aluminum sulfate, magnesium sulfate, barium sulfate, sodium hydrogen carbonate, or sodium carbonate; and an organic solvent such as acetone or methanol.
  • an acid such as nitric acid, hydrochloric acid, or sulfuric acid
  • a metal salt such as magnesium chloride, calcium chloride, sodium chloride, aluminum sulfate, magnesium sulfate, barium sulfate, sodium hydrogen carbonate, or sodium carbonate
  • an organic solvent such as acetone or methanol.
  • the shape of the component A before mixing is not particularly limited, and it can be an aqueous dispersion or powder of the PTFE that can be fibrillated as described above.
  • the powder of the PTFE that can be fibrillated include “TEFLON 6-J” (hereinbelow, “TEFLON” is a registered trademark), “TEFLON 6C-J”, “TEFLON 62-J” that are manufactured by Du Pont-Mitsui Fluorochemicals Co., Ltd., "POLYFLON F106", “POLYFLON F104", “POLYFLON F201", “POLYFLON F302” that are manufactured by Daikin Industries, Ltd., "FLUON CD123", “FLUON CD1", “FLUON CD141”, “FLUON CD145” that are manufactured by Asahi Glass Co., Ltd., and "TEFLON 60", “TEFLON 60 X”, “TEFLON 601A”, “TEFLON 601 X”, "TEFLON
  • the fine powder can be obtained by coagulation and drying of an aqueous dispersion of the PTFE that can be fibrillated, which is obtained by emulsion polymerization of TFE (that is, aqueous dispersion after finishing polymerization).
  • the aqueous dispersion of the PTFE that can be fibrillated include an aqueous dispersion after finishing the polymerization described above or an aqueous dispersion that is commercially available.
  • the preferred method for producing an aqueous dispersion of the PTFE that can be fibrillated, which is obtained after finishing the polymerization include a production method described in the publications or the like that are listed above in relation to disclosure of the homo PTFE.
  • aqueous dispersions such as "POLYFLON D-110", “POLYFLON D-210", “POLYFLON D-210C”, “POLYFLON D-310” or the like that are manufactured by Daikin Industries, Ltd., "TEFLON 31-JR", “TEFLON 34-JR” that are manufactured by Du Pont-Mitsui Fluorochemicals Co., Ltd., or "FLUON AD911L”, “FLUON AD912L”, “AD938L” that are manufactured by Asahi Glass Co., Ltd..
  • aqueous dispersion of the PTFE that can be fibrillated is added with 2 to 10 parts by weight of a non-ionic surfactant relative or the like to 100 parts by weight of PTFE in the aqueous dispersion to maintain the stability, the non-ionic surfactant may easily remain in the mixed powder which is obtained by co-coagulation, and thus it is likely to have a potential problem like coloration of a porous body.
  • an aqueous dispersion obtained after finishing the polymerization is preferred as an aqueous dispersion of the PTFE that can be fibrillated.
  • the shape of the component B before mixing is not particularly limited, but when the component B is low molecular weight PTFE, it is not particularly limited, but can be an aqueous dispersion or powder (generally referred to as PTFE micropowder or micropowder).
  • Examples of the powder of the low molecular weight PTFE include “MP1300-J” that are manufactured by Du Pont-Mitsui Fluorochemicals Co., Ltd., "LUBRON L-5”, “LUBRON L-5F” that are manufactured by Daikin Industries, Ltd., "FLUON L169J”, “FLUON L170J”, “FLUON L172J” that are manufactured by Asahi Glass Co., Ltd., and "KTL-F”, “KTL-500F” manufactured by Kitamura Limited.
  • the aqueous dispersion of the low molecular weight PTFE can be an aqueous dispersion after finishing the polymerization of the TFE as obtained by emulsion polymerization or an aqueous dispersion that is commercially available. Further, those obtained by dispersing micro powder in water by using a surfactant or the like can be also used.
  • the preferred method for producing an aqueous dispersion of the PTFE that can be fibrillated, after finishing the polymerization include a production method described in JP 7-165828 A , JP 10-147617 A , JP 2006-063140 A , JP 2009-1745 A , WO 2009/020187 A .
  • Examples of the commercially available aqueous dispersion of the PTFE that can be fibrillated include aqueous dispersions such as "LUBRON LDW-410" that are manufactured by Daikin Industries, Ltd. Because the commercially available aqueous dispersion of the low molecular weight PTFE is added with 2 to 10 parts by weight of a non-ionic surfactant relative to 100 parts by weight of PTFE in the aqueous dispersion to maintain the stability, the non-ionic surfactant or the like may easily remain in the mixed powder which is obtained by co-coagulation, and thus it is likely to have a potential problem like coloration of a porous body. For such reasons, an aqueous dispersion obtained after finishing the polymerization is preferred as an aqueous dispersion of the low molecular weight PTFE.
  • an inorganic filler is used as the component B, it is preferably an aqueous dispersion, although the shape before mixing is not particularly limited.
  • the inorganic filler include "TALC P2" manufactured by Nippon Talc Co., Ltd. and “LMR-100” manufactured by Fuji Talc Industrial Co., Ltd. They are used by dispersing powder in water after suitably performing a surface treatment using a silane coupling agent. Among them, from the viewpoint of dispersibility in water, the secondary crushed product obtained by a jet mill (for example, "TALC P2”) is preferably used.
  • the component C examples include, in addition to a fluororesin such as FEP or PFA, various resins like a non-cured silicone resin, acryl, urethane, and PET.
  • the shape before mixing is not particularly limited, but it is preferably an aqueous dispersion.
  • the aqueous dispersion in case of a resin obtained by emulsion polymerization, resin powder dispersed in water by using a surfactant or the like can be also used in addition to a dispersion which is directly usable after finishing polymerization.
  • the component C is prepared as an aqueous dispersion by dispersing a pre-determined amount in water such that it is contained at 0.1% or more but less than 20% by weight in a porous membrane.
  • the method for co-coagulation is not particularly limited. However, it is preferable to apply mechanical stirring force after mixing three aqueous dispersions.
  • an extrusion aid that is, liquid lubricant
  • the liquid lubricant is not particularly limited if it is capable of wetting the surface of PTFE powder and can be removed after molding the mixture obtained by co-coagulation into a film shape.
  • examples thereof include alcohols of hydrocarbon oil such as fluid paraffin, naphtha, white oil, toluene, or xylene, ketones, and esters.
  • the use amount of the liquid lubricant varies depending on the type of the liquid lubricant, or the like. However, it is generally 5 to 50 parts by weight relative to 100 parts by weight of the PTFE powder. By having a high use amount of the liquid lubricant, the pressure loss can be kept at low level.
  • the mixture obtained by co-coagulation is, after mixing with a liquid lubricant, extruded and rolled by a conventionally known method to be molded into a film-shaped product.
  • the extrusion can be performed by paste extrusion, ram extrusion, or the like. Preferably, it is performed by paste extrusion.
  • the rod shape extrudate extruded by paste extrusion is rolled under heating by using a calendar roll or the like under temperature condition of 40°C to 80°C, for example.
  • the thickness of the obtained rolled product in film shape is set based on the desired thickness of the porous membrane, and it is generally between 100 and 400 ⁇ m.
  • the liquid lubricant is removed from the unsintered film as a rolled product.
  • the removal of the liquid lubricant is performed by heating or extraction or a combination of them.
  • the heating temperature for the heating method is not particularly limited if it is lower than the melting point of the hot melt processable component that is not fibrillated. It is 100 to 250°C, for example.
  • the rolled product from which the liquid lubricant is removed is drawn at the temperature which is equal to or higher than the melting temperature of the hot melt processable component that is not fibrillated but is equal to or lower than the decomposition temperature of the non-hot melt processable component that is not fibrillated.
  • the hot melt processable component that is not fibrillated is melt and later hardened in the knotted portion 5, and thus the strength of the porous membrane 1 is increased in the thickness direction.
  • the temperature for drawing can be set depending on the temperature of a furnace in which the drawing is performed or the temperature of a heating roller for conveying the rolled product. Alternatively, it may be realized by combining those settings.
  • the drawing includes drawing in the first direction and drawing in the second direction which is perpendicular to the first direction.
  • the porous membrane 1 is used for a filtering medium for an air filter, it is preferable to perform also the drawing in the second direction.
  • the first direction indicates the length direction of a rolled product (that is, longitudinal direction) and the second direction indicates the width direction of a rolled product (that is, horizontal direction).
  • the rolled product is drawn at elongation area ratio of 40 to 800 times.
  • the drawing speed in the first direction is preferably 10 to 600%/second, and more preferably 10 to 150%/second.
  • the temperature at the time of drawing is preferably 200 to 350°C, and more preferably 280 to 310°C.
  • the drawing speed in the second direction is preferably 10 to 600%/second.
  • the temperature at the time of drawing is preferably 200 to 400°C, and more preferably 250 to 350°C.
  • the drawing in the second direction can be performed either simultaneously or separately with the drawing in the first direction.
  • the temperature, drawing ratio, and drawing speed at the time of drawing are known to have an effect on the physical properties of a drawn product.
  • the S-S curve of the unsintered PTFE product (that is, graph illustrating the relationship between tensile strength and elongation) exhibits specific characteristics that are different from those of other resins.
  • the resin material illustrates increased tensile strength in accordance with elongation.
  • the range of elastic range and break point vary depending on materials and conditions for evaluation. However, it is very common that the tensile strength exhibits increasing tendency in accordance with the elongation amount.
  • the tensile strength of the unsintered PTFE product exhibits a gradual decrease tendency after illustrating a peak at a certain elongation amount. It represents the presence of a "region in which an undrawn part becomes weaker than a drawn part" in an unsintered PTFE product.
  • the drawing speed of the first drawing is 150%/second or less, and preferably 80%/second or less and the drawing in the second direction is 500%/second or less when conventional PTFE is used only as a raw material.
  • the structure of the molded article with low filling ratio, which is obtained as above, is easily damaged by external force.
  • the above phenomenon caused by low drawing speed becomes more significant.
  • the drawing speed of the first drawing could increase to 600%/second or less, and preferably 150%/second or less, and the drawing speed in the second direction could increase to 600%/second or less.
  • the hot melt processable component that is not fibrillated it becomes possible to maintain the structure even after the post processing.
  • the porous membrane 1 obtained accordingly is thermally fixed to obtain increased strength or dimensional stability.
  • the temperature for thermal fixing can be equal to or higher, or lower than the melting temperature of PTFE, and it is preferably 250 to 400°C.
  • Fig. 3 is a drawing illustrating the cross section of the filtering medium 9 for an air filter of this embodiment in thickness-direction.
  • Fig. 5 is a drawing illustrating the cross section of the filtering medium 10 for an air filter of this embodiment in thickness-direction.
  • Fig. 5 illustrates the filtering medium with a five layer structure.
  • the filtering medium 10 for an air filter is a filtering medium for an air filter which includes one or more porous membrane 1 having PTFE as a main component and a plurality of air permeable supports 13 which supports the porous membrane 1 and is arranged at least on the outermost layer, in which the pressure loss when air is passed through at a flow rate of 5.3 cm/sec is less than 200 Pa, the PF value represented by the following equation is 17 or higher when air containing NaCl particles with particle diameter of 0.3 ⁇ m is passed through at a flow rate of 5.3 cm/sec, the dust holding capacity of polyalphaolefin particles is 20 g/m 2 or more when air containing polyalphaolefin particles with a count median diameter of 0.25 ⁇ m is continuously passed through at a flow rate of 5.3 cm/sec and pressure loss is increased to 250 Pa, and the membrane thickness of one piece of the porous membrane described above is 30 ⁇ m or more.
  • PF ⁇ log Transmittance % / 100 / Pressure loss Pa
  • the pressure loss described herein indicates the initial pressure loss.
  • the "initial” means a time point at which the filtering medium for an air filter is hold on a frame body to give an air filter unit and it become a usable state after installing it at a pre-determined location.
  • the filtering medium 9 or 10 for an air filter includes one or more porous membrane 1 and a plurality of air permeable supports 13 as described above.
  • the filtering medium 9 illustrated in Fig. 3 has a three layer structure with one piece of the porous membrane 1 and two pieces of the air permeable support 13 having the porous membrane 1 between them.
  • the filtering medium 10 illustrated in Fig. 5 has a five layer structure in which two pieces of the porous membrane 1 and three pieces of the air permeable support 13 are laminated alternately.
  • Fig. 2 is a drawing describing the structure of the porous membrane 1 of the filtering medium 9 or 10.
  • the porous membrane 1 includes the polytetrafluoroethylene that can be fibrillated, the non-hot melt processable component that is not fibrillated, and the hot melt processable component with a melting point of lower than 320°C that is not fibrillated.
  • Each of those components is the same as the polytetrafluoroethylene that can be fibrillated, the non-hot melt processable component that is not fibrillated, and the hot melt processable component with a melting point of lower than 320°C that is not fibrillated, which have been described in the first embodiment.
  • the content of the hot melt processable component that is not fibrillated is preferably 10% by weight or less.
  • the filling ratio of porous membrane 1 which is calculated according to the following equation, is preferably 1 to 20%, and more preferably 2 to 10%.
  • Filling ratio % Specific gravity of porous membrane / Specific gravity of raw material ⁇ 100
  • Specific gravity of porous membrane Weight of porous membrane / Membrane thickness of porous membrane ⁇ Area of porous membrane
  • the specific gravity of the raw material is represented by a value obtained by dividing the sum of the product of specific gravity of each component with weight ratio of each component by the sum of the weight ratio, in case of a mixed raw materials which include plural components.
  • Membrane thickness of the porous membrane 1 is 30 ⁇ m or more. As described herein, the membrane thickness means the membrane thickness of a single piece of the porous membrane 1. When the filtering medium has one or more porous membrane 1, it indicates the membrane thickness of each layer.
  • the membrane thickness of the porous membrane 1 is preferably 35 ⁇ m or more, and more preferably 40 ⁇ m or more. From the viewpoint of having the pressure loss of less than 200 Pa for the filtering medium, the membrane thickness is preferably 250 ⁇ m or less and more preferably 200 ⁇ m or less.
  • the membrane thickness is measured by using a membrane thickness meter. With the membrane thickness being equal to or less than the upper limit of the above range, an increase in the pressure loss of the filtering medium is suppressed.
  • the knotted portion 5 By containing a pre-determined amount of the melt processable component that is not fibrillated in the porous membrane 1 and hardening of the component in the knotted portion 5, the knotted portion 5 becomes hard and thus it is not squashed even when compressive force or the like is applied in a membrane thickness direction during a post step. Accordingly, the membrane thickness can be maintained. As the occurrence of a fiber with thin fiber diameter is suppressed as described above, the porous membrane 1 has a structure with many voids in which overlapping of fibers is reduced.
  • the collection efficiency compared at the same membrane thickness is lowered compared to a porous PTFE membrane of a related art in which the non-hot melt processable component that is not fibrillated is not contained,.
  • the strength in the thickness direction of the porous membrane 1 is increased so that the volume can be increased to the aforementioned membrane thickness range compared to a porous PTFE membrane of a related art in which the hot melt processable component that is not fibrillated is not contained. Accordingly, the fiber amount increases in the thickness direction of the porous membrane 1, and thus not only a negative influence of the collection efficiency is suppressed but also the dust holding capacity can be significantly increased due to the membrane structure having many voids while inhibiting an increase in the pressure loss.
  • the porous PTFE membrane when drawn at high ratio to lower the pressure loss, the density difference in a thin fiber which is generated between different regions in the same filtering medium is increased, yielding a high deviation in the pressure difference.
  • the deviation in the pressure difference described herein means a deviation in pressure difference between different regions in the same filtering medium.
  • the volume can be increased by maintaining the pressure loss at low level by drawing at low ratio and the deviation in pressure loss can be maintained at low level while significantly increasing the dust holding capacity. Further, by containing the hot melt processable component that is not fibrillated, the structure with high volume can be maintained even when external force is applied thereto.
  • a porous PTFE membrane of a related art contains lots of tiny fibrils with thin fiber diameter so that the surface area per fibril is high and the collection efficiency per fiber is high.
  • the membrane thickness is thin, there are many overlapping of the fibers, and thus it is impossible to hold many fine particles. As a result, the extent of the collection efficiency per fiber is not effectively exhibited.
  • the membrane thickness is increased in the porous membrane 1 of this embodiment, the amount of fiber with thin fiber diameter is reduced but the amount of the relatively thick fiber and the amount of the void that are formed by those thick fibers in the porous membrane 1 are increased, and thus a fiber structure capable of increasing the dust holding capacity while suppressing an increase in the pressure loss or a decrease in the collection efficiency is obtained.
  • a region having thin fiber diameter and a large amount of fiber and a region having thick fiber diameter and a small amount of fiber are mixedly present in a filtering medium with a structure in which the deviation in fiber diameter is high, a region with improved dust holding capacity is partially present.
  • a filtering medium is adjoined to a unit, for example, it is expected that the average dust holding amount on a large area of the filtering medium is expected to be insufficiently improved, because the influence of a region having low dust holding capacity as having many thin fibers is high.
  • the shape is greatly changed from a round rod shape to a sheet shape when it is processed into a sheet shape during rolling. At that time, the extrudate is more significantly squashed in an area closer to the center part of a cross section of the round rod shape.
  • the part showing behavior that is different from other parts that is, rolling behavior
  • the extruded shape has a sheet shape, the shape change is small during the extrusion and the whole extrudate is squashed during rolling.
  • one or more layers of the porous membrane 1 can be contained in the filtering medium 9 to 11 for an air filter. Further, when a plurality of layers of the porous membrane 1 is contained, the porous membrane 1 can be directly laminated to each other or laminated as intermediated by the air permeable support 13. In that case, the air permeable support 13 can be a single layer or plural layers in which plural pieces are overlaid. Further, when plural layer of the porous membrane 1 are contained and the air permeable support 13 is interposed between the neighboring two porous membrane 1, the air permeable support 13 can be the same kind or different kind compared to the air permeable support 13 that is disposed on the outermost layer of the filtering medium 10 for an air filter.
  • the air permeable support 13 is the same as the air permeable support described in the first embodiment.
  • One more layer of the air permeable support 13 may be contained in the filtering medium 10 for an air filter in addition to the outermost layer.
  • the air permeable support 13 contained in the filtering medium 10 for an air filter can be the same kind or different kind.
  • the air permeable support 13 can be adhered to the porous membrane 1 by using the anchor effect based on partial melt of the air permeable support 13 by heating or melt of the hot melt resin or by using the adhesion using reactive adhesives or the like.
  • the layer structure of the filtering medium can be determined so as to achieve the collecting performance of the HEPA filter based on JIS Z8122, that is, an air filter having particle collecting ratio of 99.97% or more for the particles with particle diameter of 0.3 ⁇ m under standard wind amount and initial pressure loss of 245 Pa or lower.
  • the layer structure of the filtering medium can be a three layer structure like the filtering medium 9 illustrated in Fig. 3 , a five layer structure like the filtering medium 10 illustrated in Fig. 5 , a four layer structure like the filtering medium 11 illustrated in Fig. 6 , or a six or higher layer structure.
  • Fig. 6 is a drawing illustrating the cross section of the filtering medium in thickness direction, in which the filtering medium is according to a variation example of this embodiment.
  • each of the porous membrane 1 has average fiber diameter of 0.10 to 0.12 ⁇ m, membrane thickness of 35 to 60 ⁇ m, and filling ratio of 3 to 5%, and the filtering medium 10 has membrane thickness of 400 to 500 ⁇ m, for example.
  • the filtering medium 11 with four layer structure illustrated in Fig. 6 is obtained by disposing two pieces of the air permeable support 13 on the outside of two pieces of the porous membrane 1 that are directly laminated on each other.
  • Fig. 6 is a drawing illustrating the cross section of the filtering medium in thickness direction, in which the filtering medium is according to a variation example of this embodiment.
  • each of the porous membrane 1 has average fiber diameter of 0.10 to 0.12 ⁇ m, membrane thickness of 35 to 60 ⁇ m, filling ratio of 3 to 5%, and average pore diameter of 0.8 to 1.6 ⁇ m.
  • the filtering medium 11 has membrane thickness of 400 to 500 ⁇ m, for example.
  • the filtering medium having the collecting performance as a HEPA filter is not limited to those having a layer structure illustrated in Fig. 1 , Fig. 3 , or Fig. 6 .
  • the upper limit of the layer number in layer structure is determined within a region in which the pressure loss as a HEPA filter is not deteriorated.
  • the filtering medium of this embodiment has a pressure loss of less than 200 Pa as described above.
  • the structure of the porous membrane 1 is a structure in which an occurrence of fiber with thin fiber diameter is suppressed and voids are present in a large amount as described above, the pressure loss of the porous membrane 1 is maintained at low level, and as a result, the pressure loss as a filtering medium is maintained at the level of less than 200 Pa.
  • the PF value of the filtering medium of this embodiment is 17 or higher.
  • the structure of the porous membrane 1 is a structure with many voids and high volume having high membrane thickness, a decrease in collection efficiency of the porous membrane 1 is suppressed, and as a result, the collection efficiency as a filtering medium is high and the pressure loss is low. Accordingly, the PF value of 17 or higher is achieved.
  • the dust holding capacity of the filtering medium of this embodiment is 20 g/m 2 or higher. Because the dust holding capacity of the porous membrane 1 can be increased as described above, the dust holding capacity of 20 g/m 2 or higher is obtained for the filtering medium.
  • the dust holding capacity is evaluated by pressure loss build-up test at the time of passage of PAO particles.
  • the PAO particles are preferably used as a test particle from the viewpoint of being widely used compared to solid particles like NaCl.
  • the filtering medium of this embodiment preferably has collection efficiency of 99.97% or more when air including test particles, which are defined by the method for testing the performance of a filtering medium for an air filter used for a clean room as described in the attachment of JIS B9927, is continuously passed at a flow rate of 5.3 cm/second.
  • test particles which are defined by the method for testing the performance of a filtering medium for an air filter used for a clean room as described in the attachment of JIS B9927
  • the filtering medium of this embodiment preferably has variation coefficient CV of 5 % or less, in which the variation coefficient CV is obtained by dividing the standard deviation of pressure loss distribution by an average value.
  • the lower limit of the variation coefficient CV is 1%, for example.
  • the pressure loss distribution of a filtering medium is obtained by dividing the filtering medium into 100 lattices and measuring the pressure loss in an area with diameter of 100 mm within each lattice.
  • the measurement of pressure loss can be performed by using a measurement device equipped with a manometer for performing the measurement of the two surfaces of the filtering medium 10 while it is brought close to the surface of the filtering medium and operating the manometer such that it can move along the pre-determined path on the surface at downstream side of each region.
  • the filtering medium for an air filter of the present invention has an area from which plural pieces can be cut out to be used for plural air filter units. It is generally a long piece which is longer in length direction.
  • the size of the filtering medium is not particularly limited. However, the length in the length direction is 100 to 1000 m and the length in the width direction is 600 to 2000 mm.
  • the variation coefficient CV of pressure loss of the filtering medium according to this embodiment is 5% or less compared to the variation coefficient of 10% or so of a porous PTFE membrane of a relate art, which includes homo PTFE. It also has suppressed deviation in pressure loss.
  • the porous PTFE membrane of a related art has low film thickness due to high drawing ratio, a region with low pressure loss due to heterogeneous drawing occurs, and due to the presence of a region with low pressure loss, the collection efficiency is lowered.
  • lowering the drawing ratio at the time of manufacturing the porous membrane can be considered. However, simply lowering the drawing ratio may cause other problem like increased pressure loss.
  • a porous membrane having high film thickness due to high average fiber diameter and fiber structure with many voids can be obtained by using a raw material for a porous membrane which contains the non-hot melt processable component that is not fibrillated and the hot melt processable component that is not fibrillated in addition to PTFE that can be fibrillated.
  • the filtering medium of this embodiment has pressure loss which is suppressed to a low value of less than 200 Pa, and together with low deviation in pressure loss, it has increased dust holding capacity.
  • the dust holding capacity of the filtering medium as a whole is not an average of the region with high dust holding capacity and the region with low dust holding capacity, but it is believed to be lower as dominated by the region with low dust holding capacity.
  • the variation coefficient CV of the pressure loss is preferably 5% or less.
  • the filtering medium is a filtering medium for an air filter having a collecting performance as a HEPA filter, which includes the porous membrane 1 having PTFE as a main component and the air permeable support 13.
  • the filtering medium has dust holding capacity of 20 g/m 2 or more and the membrane thickness of the porous membrane 1 is 30 ⁇ m or more.
  • the porous PTFE membrane of a related art has a disadvantage that, although the initial collection efficiency is high, the dust holding capacity is small due to a fiber stricture having many fibers with small fiber diameter.
  • the porous membrane 1 of the filtering medium of this embodiment has a larger average fiber diameter and a fiber structure with larger gap between fibers compared to the porous PTFE membrane of a related art, and due to high membrane thickness, it has a fiber structure in which the amount of fiber having high fiber diameter is increased and a great amount of voids is present (with low filling ratio).
  • the filtering medium of this embodiment has excellent dust holding capacity like a filtering medium including glass fiber by satisfying the collecting performance as a HEPA filter as it maintains the pressure loss at low level while suppressing an adverse effect on the initial collection efficiency which is caused by large average fiber diameter. This performance and fiber structure are not obtained from a filtering medium in which a porous PTFE membrane of a related art, which includes homo PTFE, is used.
  • the filtering medium is not required to be formed with a pre-collecting layer which includes a melt-blown non-woven fabric or the like. Since a filtering medium for an air filter of a related art has a thinly drawn porous PTFE membrane and the liquid particles have small dust holding capacity, in order to increase the dust holding capacity of liquid particles, a filtering medium obtained by adhering a melt-blown (MB) fabric including polypropylene (PP) with thickness of 300 ⁇ m on the upstream side of the porous PTFE membrane has been suggested. However, this type of the filtering medium generates impurities from the melt-blown non-woven fabric, and thus it is likely to contaminate passing air flow.
  • MB melt-blown
  • PP polypropylene
  • the filtering medium of this embodiment has high dust holding capacity as described above, the generation of impurities from a pre-collecting layer does not occur. Further, because it is unnecessary to form a pre-collecting layer, it is possible to ensure the area for inserting the folded filtering medium to the frame body at the time of manufacturing an air filter unit.
  • the filtering medium of the present embodiment is used for the uses and fields that are the same as those described for the first embodiment, except the field of liquid filtration.
  • the air filter unit is the same as the air filter unit illustrated in Fig. 4 , which has been described in the first embodiment.
  • the aforementioned filtering medium 9, the filtering medium 10, or the filtering medium 11 is used for the processed filtering medium 21.
  • the air filter unit using any one of the filtering medium 9 to 11 is not limited to the air filter unit 20 illustrated in Fig. 4 , and it can be other type like the air filter unit 30 of V bank type illustrated in Fig. 7 (also referred to as double pleats type), or the like.
  • Fig. 7 is a dimensional view illustrating the air filter unit 30 of V bank type which has been partially cut out.
  • the air filter unit 30 includes the filtering medium 31, the pack receiver 37 and 39, and the frame body 34.
  • the aforementioned filtering medium 9, the filtering medium 10, or the filtering medium 11 is used for the filtering medium 31, the aforementioned filtering medium 9, the filtering medium 10, or the filtering medium 11 is used.
  • the filtering medium 31 is obtained by performing a pleats processing of a sheet shape to zigzag shape, and by optionally providing a spacer composed of a hot melt resin or the like, it is processed into a filter pack.
  • Plural filter packs are disposed inside the frame body 34 such that plural V-letter shapes are arranged in single direction, the end part of the airflow inlet side is supported by the pack receiver 37, and the end part of the outlet side is supported by the pack receiver 39.
  • the air filter unit uses any one of the filtering medium 9 to 11 described above and it is manufactured as an air filter unit of the aforementioned mini pleats type.
  • the air filter unit 20 and 30 has suppressed decrease in collecting performance even though the dust holding capacity is as large as that of the filtering medium including glass fiber. Further, by having high dust holding capacity, it is unnecessary to provide a pre-collecting layer, and thus it is possible to ensure the area for inserting the folded filtering medium to the frame body at the time of manufacturing an air filter unit without having impurities that are conventionally generated from a pre-collecting layer.
  • the method for manufacturing a filtering medium for an air filter includes a step of performing co-coagulation (ST10), a step of performing paste extrusion (ST20), a step of performing rolling (ST30), a step of performing drawing (ST40), and a step of performing lamination (ST50).
  • the step of performing co-coagulation (ST10) to the step of performing drawing (ST40) correspond to one example of the method for manufacturing a porous membrane of this embodiment. Accordingly, a porous membrane is manufactured.
  • a material for molding which is a raw material of the porous membrane, is manufactured.
  • the method for manufacturing a material for molding including the method for manufacturing a material for molding, which is performed during the step (ST10) for performing co-coagulation, is described.
  • descriptions are given by having PTFE that can be fibrillated as the component A, the non-hot melt processable component that is not fibrillated as the component B, and the hot melt processable component that is not fibrillated as the component C.
  • the component B is a component having thermoplastic property like low molecular weight PTFE.
  • the material for molding can be prepared as a composition like the mixed powder, and it can be manufactured various methods including the step of performing co-coagulation (ST10).
  • the composition when the composition is mixed powder, there can be a method in which powder of each of the component A, the component B, and the component C is mixed using a common mixture or the like, a method obtaining co-coagulated powder by co-coagulation of aqueous dispersions each containing the component A, the component B, or the component C (that is, step of performing c-coagulation (ST10)), a method in which mixed powder obtained by co-coagulating in advance of an aqueous dispersion of any two components of the component A, the component B, and the component C with powder of the remaining one component by using a common mixer or the like, or the like.
  • Desirable materials for performing the drawing can be obtained by any one of those methods. Among them, from the viewpoint of easy and homogeneous dispersion of the three different components, co-coagulating aqueous dispersions each containing the component A, the component B, or the component C, that is, obtaining by the step of performing co-coagulation (ST10), is preferable.
  • Examples of the co-coagulating method including the step of performing co-coagulation (ST10) include the method (i) to (iv) which have been described for the first embodiment. Among them, from the viewpoint of easy and homogeneous dispersion of the three components, the method (i) is preferable.
  • the coagulation is preferably performed by adding an acid, a metal salt, or an organic solvent as it has been described in the first embodiment.
  • the shape of the component A before mixing is not particularly limited, but it is preferably an aqueous dispersion of high molecular weight PTFE described above.
  • the high molecular weight PTFE include an aqueous dispersion like a commercially available product of high molecular weight PTFE which has been listed in the first embodiment.
  • the shape of the component B before mixing is not particularly limited, but it is preferably an aqueous dispersion when the component B is low molecular weight PTFE.
  • the aqueous dispersion can be, in addition to an aqueous dispersion obtained by emulsion polymerization, molding powder or fine powder dispersed in water by using a surfactant of the like. Among them, from the viewpoint of the stability of an aqueous dispersion, an aqueous dispersion obtained by emulsion polymerization is preferably used.
  • the low molecular weight PTFE include a commercially available product of low molecular weight PTFE or the like which has been listed in the first embodiment.
  • the shape of the component B before mixing is preferably an aqueous dispersion.
  • the inorganic filler include the commercially available product of inorganic fillers or the like which are listed in the first embodiment. They are used by dispersing powder in water after suitably performing a surface treatment using a silane coupling agent or the like, or the like. Among them, from the viewpoint of dispersibility in water, the secondary crushed product obtained by a jet mill (for example, "TALC P2”) is preferably used.
  • the component C examples include each resin of non-cured silicone resin, acryl, urethane, and PET or the like in addition to a fluororesin like FEP and PFA.
  • the shape before mixing is not particularly limited, but is it preferably an aqueous dispersion.
  • the aqueous dispersion in case of a resin obtained by emulsion polymerization, resin powder dispersed in water by using a surfactant or the like can be also used in addition to a dispersion directly usable after finishing polymerization.
  • the hot melt processable component that is not fibrillated is prepared as an aqueous dispersion by dispersing a pre-determined amount in water such that it is contained at 0.1% or more but less than 20% by weight in a porous membrane.
  • the method for co-coagulation it is preferable to apply mechanical stirring force after mixing three aqueous dispersions.
  • the aforementioned acid, metal salt, organic solvent, or the like can be also used as a coagulating agent.
  • an extrusion aid that is, liquid lubricant
  • the type and use amount of the liquid lubricant are the same as those described in the first embodiment.
  • the mixture obtained by co-coagulation is, after mixing with a liquid lubricant, extruded and rolled by a conventionally known method to be molded into a film shape product.
  • the extrusion can be performed by paste extrusion (ST20), ram extrusion, or the like. Preferably, it is performed by paste extrusion.
  • the rod shape extrudate extruded by paste extrusion is rolled under heating by using a calendar roll or the like under temperature condition of 40°C to 80°C, for example (ST30).
  • the thickness of the obtained rolled product in film shape is set based on the desired thickness of the porous membrane, and it is generally between 100 and 400 ⁇ m.
  • the rod shape examples include a sheet shape, a column shape (also referred to as a round rod shape), or the like, which are elongated in one direction.
  • the extrudate in rod shape is preferably in a sheet shape.
  • a sheet shape morphological change is small when an unsintered film (also referred to as a raw tape) is subjected to a rolling processing so that a homogeneous raw tape can be easily obtained.
  • the physical properties are homogeneous after processing into a porous membrane (also referred to as a drawn membrane) so that a porous membrane having little deviation in pressure loss when used for a filtering medium for an air filter can be obtained.
  • the extrudate in sheet shape is formed by extruding from a sheet die (T die) which is installed on the tip of a paste extruder.
  • the paste extruder has a round hole formed on the tip part, for connection to the internal space.
  • the sheet die is formed with an extrusion hole, which is formed in rectangular shape when viewed from the direction in which the extrudate is extruded. For example, it has an extrusion hole having a size with length of 100 to 250 mm in length direction and length of 1 to 8 mm in width direction. According to extrusion from an extrusion hole with such shape, the extrudate is extruded in sheet shape. Meanwhile, by detaching the sheet die from a paste extruder, the extrudate is extruded in column shape.
  • the liquid lubricant is removed from an unsintered film as a rolled product. Removal of the liquid lubricant is performed in the same manner as those described in the first embodiment.
  • the extrudate from which the liquid lubricant is removed is drawn at a temperature which is equal to or higher than the melting temperature of the hot melt processable component that is not fibrillated but is equal to or lower than the decomposition temperature of the non-hot melt processable component that is not fibrillated (ST40).
  • the component C is melt and later hardened in the knotted portions so that the strength of the porous membrane is increased in the thickness direction.
  • the temperature for drawing can be set depending on the temperature of a furnace in which the drawing is performed or the temperature of a heating roller for conveying the rolled product. Alternatively, it may be realized by combining those settings.
  • the drawing in length direction can be performed by using an apparatus illustrated in Fig. 5 of JP 2012-020274 A , for example. Further, the drawing in width direction can be performed with the left half part (tenter) of the apparatus illustrated in Fig. 6 of JP 2012-020274 A , for example.
  • the drawing includes drawing in the length direction (MD direction) of an extrudate and drawing in the width direction (TD direction) which is preferably perpendicular to the length direction.
  • MD direction length direction
  • TD direction width direction
  • the porous membrane is used for a filtering medium for an air filter, it is preferable to perform also the drawing in the width direction.
  • the rolled product is drawn at elongation area ratio of 40 or more but less than 150 times.
  • the drawing ratio in the length direction is 4 or more but less than 10 times.
  • Each of the drawing speed in the length direction and drawing temperature has the same condition as those described in the first embodiment.
  • the drawing ratio in the width direction is more than 10 but less than 25 times.
  • the drawing ratio in the width direction is equal to or less than 10 times, the drawing cannot be performed favorably so that it becomes difficult to obtain a homogeneous porous membrane.
  • Each of the drawing speed in the width direction and drawing temperature has the same condition as those described in the first embodiment.
  • the drawing in the width direction can be performed either simultaneously or separately with the drawing in the length direction.
  • the porous membrane obtained accordingly is preferably subjected to thermal fixing to obtain increased strength or dimensional stability.
  • the temperature at the time of thermal fixing can be equal to or higher, or lower than the melting point of PTFE. It is preferably 250 to 400°C.
  • an air permeable support is laminated on the obtained porous membrane.
  • a non-woven fabric, a woven fabric, a metal mesh, a resin net, or the like which have been described above can be used as the air permeable support.
  • the lamination can be performed by a conventionally known method.
  • adhesion of the air permeable support 13 to the porous membrane 1 can be achieved by using the anchor effect based on partial melt of the air permeable support 13 by heating or melt of a hot melt resin or by using the adhesion with reactive adhesives.
  • Such lamination can be performed with the right half part (thermal lamination apparatus) of the apparatus illustrated in Fig. 6 of JP 2012-020274 A , for example. Further, the lamination between the porous membranes is performed as described in Example 4 with heating to around the melting temperature of PTFE.
  • a filtering medium for an air filter having high dust holding capacity so as to have suppressed decrease in collecting performance and no occurrence of impurities is obtained.
  • the filtering medium for an air filter of a related art which is used for a HEPA filter for air injection is required to have a low pressure loss value like 80 to 140 Pa or so.
  • the porous PTFE membrane of a related art, which includes homo PTFE has a thin membrane thickness even though the collection efficiency is high. Thus, even when a filtering medium with five layer structure as illustrated in Fig. 3 is manufactured, for example, the dust holding capacity is insufficient.
  • a porous membrane with large average fiber diameter and high membrane thickness and a fiber structure that is different from that of a porous PTFE membrane of a related art is obtained.
  • the drawing ratio is high during manufacture of a porous membrane, the performance is deteriorated due to decreasing membrane thickness and also the collection efficiency is low for a porous membrane with single layer.
  • a filtering medium for an air filter which does not exist before and has a low pressure loss and significantly improved dust holding capacity without compromising the performance is obtained.
  • the hydrocarbon oil (manufactured by Idemitsu Kosan Co., Ltd., "IP SOLVENT 2028") was added at 20°C to the mixture in an amount of 25 parts by weight per 100 parts by weight of the mixture followed by mixing.
  • the obtained mixture was extruded using a paste extruder to obtain a molded product with a round rod shape.
  • the molded product with a round rod shape was molded into a film shape using a calendar roll heated to 250°C to obtain a PTFE film.
  • the film was passed through a heat wave drying furnace at 250°C to remove the hydrocarbon oil by evaporation, thus obtaining an unsintered band-shaped PTFE film having average thickness of 200 ⁇ m and average width of 150 mm.
  • the unsintered PTFE film was drawn in the length direction at drawing ratio of 5 times and drawing speed of 38%/second.
  • the drawing temperature was 300°C.
  • the drawn but unsintered film was drawn in the width direction at drawing ratio of 13.5 times and drawing speed of 330%/second by using a tenter capable of continuous clipping followed by thermal fixing. At that time, the drawing temperature was 290°C and the temperature for thermal fixing was 390°C. Accordingly, a porous membrane (filling ratio of 4.2%, average fiber diameter of 0.150 ⁇ m, and thickness of 38.6 ⁇ m) was obtained.
  • a spun-bond non-woven fabric (average fiber diameter of 24 ⁇ m, weight per unit area of 40 g/m 2 , and thickness of 0.2 mm), which includes a fiber having a core/sheath structure in which PET is used for the core and PE is used for the sheath, was laminated as an air permeable support on both sides of the obtained porous membrane 1 by thermal fixing using a lamination apparatus.
  • a filtering medium was obtained.
  • Performances of the porous membrane and filtering medium as obtained above that is, a pressure loss, a PF value, filter life span, membrane thickness decreasing rate, and dust holding capacity, and the like, were calculated.
  • Example 2 The processing and evaluation were made in the same manner as Example 1 except that an inorganic filler ("TALC P2" manufactured by Nippon Talc Co., Ltd.) is used instead of the PTFE aqueous dispersion with melt viscosity of 20000 Pa ⁇ s (PTFE-B) measured by a flow tester method at 380°C, the liquid lubricant is used at 29 parts by weight, and the drawing ratio in the width direction is changed to 20 times.
  • an inorganic filler (“TALC P2" manufactured by Nippon Talc Co., Ltd.
  • PTFE-B melt viscosity of 20000 Pa ⁇ s
  • the porous membrane and filtering medium were obtained and the filter performance was determined in the same manner as Example 1 by using PTFE aqueous dispersion (PTFE-A) with SSG of 2.160 except that the non-hot melt processable component that is not fibrillated and the hot melt processable component that is not fibrillated are not used, the liquid lubricant is used at 30 parts by weight, and the drawing ratio in the width direction is changed to 24 times.
  • PTFE-A aqueous dispersion
  • SSG SSG of 2.160
  • Example 2 The processing and evaluation were made in the same manner as Example 1 except that the hot melt processable component that is not fibrillated is not used, the mixing ratio of PTFE that can be fibrillated and the non-hot melt processable component that is not fibrillated is changed (that is, 70% by weight of PTFE that can be fibrillated and 30% by weight of the non-hot melt processable component that is not fibrillated), and the drawing ratio in the width direction is changed to 20 times.
  • Example 2 The processing and evaluation were made in the same manner as Example 1 except that the non-hot melt processable component that is not fibrillated is not used, the mixing ratio polytetrafluoroethylene that can be fibrillated and the hot melt processable component that is not fibrillated is changed (that is, 90% by weight of PTFE that can be fibrillated and 10% by weight of the hot melt processable component that is not fibrillated), and the drawing ratio in the width direction is changed to 20 times.
  • Example 1 The processing and evaluation were made in the same manner as Example 1 except that the mixing ratio of each component in Example 1 is changed such that content of the hot melt processable component that is not fibrillated is 23% by weight.
  • Example 1 The processing and evaluation were made in the same manner as Example 1 except that the drawing temperature of Example 1 is changed to a temperature which is equal to or lower than the melting point of the hot melt processable component that is not fibrillated.
  • Example 2 The processing and evaluation were made in the same manner as Example 1 except that, with regard to Example 1, a silicone resin ("G-600” manufactured by Gamma Chemical Co., Ltd) is used as the hot melt processable component that is not fibrillated.
  • a silicone resin ("G-600” manufactured by Gamma Chemical Co., Ltd) is used as the hot melt processable component that is not fibrillated.
  • a disc-shaped test sample having an effective area of 100 cm 2 was taken from the porous membrane 1.
  • the pressure was measured at the upstream side and downstream side of the test sample by using a manometer.
  • the difference in pressure between the upstream side and downstream side was obtained as a pressure loss of the porous membrane 1.
  • the pressure loss was similarly obtained.
  • the air filter unit 20 was set in a rectangular duct for test, the air flow was adjusted to have wind flow amount of 56 m 3 /minute, and the pressure was measured at the upstream side and downstream side of the air filter unit 20 by using a manometer. The difference in pressure between the upstream side and downstream side was obtained as a pressure loss of the air filter unit 20. Meanwhile, a separator type with 610 mm (length) ⁇ 610 mm (width) x 290 mm (inner length) was used as the air filter unit 20.
  • the collection efficiency was also calculated by using the filtering medium which was manufactured by using the same porous membrane.
  • PF values were obtained by using NaCl particles with particle diameter of 0.3 ⁇ m according to the following equation in view of the pressure loss and the collection efficiency (NaCl 0.3 ⁇ m) of the porous medium.
  • PF value ⁇ log Transmittance % / 100 / Pressure loss Pa ⁇ 1000
  • the PF value was also calculated by using the filtering medium which was manufactured by using the same porous membrane.
  • the amount of NaCl particles (g/m 2 ) which was supplied until the pressure loss of the porous membrane is increased to 100 Pa was measured, and it was taken as the life span of the porous membrane.
  • the effective filtering area of the porous membrane used was 50 cm 2 .
  • the pressure loss was measured as described above.
  • the amount of the NaCl particles was obtained by subtracting the initial mass from the mass of the sample filtering medium after the increase of 100 Pa according to the test.
  • the life span (g/m 2 ) was also calculated by using the filtering medium which was manufactured by using the same porous membrane.
  • the air filter unit 20 of a separator type with 610 mm (length) ⁇ 610 mm (width) ⁇ 290 mm (inner length) was produced and installed in a test duct.
  • the filtering medium a medium undergone the pleats processing with a folded and inserted area of 24 m 2 was used.
  • the membrane thickness change with application of pressure of 6.4 kPa in a direction which is perpendicular to the membrane surface was continuously (0.1 Hz) recorded by using a data logger.
  • the membrane thickness decreasing amount during 0.5 seconds after the detector contacts the membrane was measured from the recorded data, and the membrane thickness decreasing rate ( ⁇ m/second) was calculated.
  • the consumed power (kWh) was calculated as powder consumption amount accompanied with ventilation.
  • the initial pressure loss value was used.
  • Power consumption kWh Wind amount m 3 / minute ⁇ Pressure loss Pa ⁇ Ventilation time h / Fan efficiency ⁇ ⁇ 100
  • the energy saving effect (1000 yen/year) for the case of using the air filter unit 20 compared to a case of using an air filter unit in which a filtering medium made of glass fiber was calculated according to the following procedures.
  • Comparative Example 1 not containing the non-hot melt processable component that is not fibrillated and the hot melt processable component that is not fibrillated showed significantly lowered pressure loss, PF value, and filter life span according to the lamination of an air permeable support, indicating a deterioration of filter performance.
  • the membrane thickness decreasing rate was also high and the strength of the porous membrane was insufficient.
  • Comparative Example 2 not containing the hot melt processable component that is not fibrillated and Comparative Example 3 not containing the non-hot melt processable component that is not fibrillated allow the manufacture of a porous membrane having the filling ratio that is almost the same as that of Example 1.
  • the pressure loss or the like was significantly lowered like Comparative Example 1, indicating a deterioration of filter performance.
  • the membrane thickness decreasing rate was also high and the strength of the porous membrane was insufficient.
  • Example 5 By using the filtering medium prepared in Example 1, an air filter unit of separator type was manufactured (Example 5) and it was compared to the air filter unit (Comparative Examples 6 and 7), which was manufactured by using a filtering medium of a related art, in terms of pressure loss and life span.
  • a processed filtering medium with a zigzag shape was produced by subjecting each filtering medium to a pleats processing with a rotary type folding machine such that it can have outer folding and inner folding at every 260 nm in the length direction. Then, a separator obtained by corrugation processing of an aluminum plate was inserted to a valley part of the filtering medium to obtain a filter pack with length of 590 mm x width of 590 mm. The number of pleats was 160 (80 peaks).
  • the obtained filter pack was fixed onto a frame body made of aluminum having outer dimension as follows: 610 mm (length) ⁇ 610 mm (width) ⁇ 290 mm (inner length). Periphery of the filter pack was attached to the frame body with urethane adhesives. The pressure loss, filter life span, power consumption amount, and energy saving effect of the air filter unit were calculated.
  • Comparative Example 6 the processing and evaluation were made in the same manner as Example 5 except that, instead of a filtering medium and a separator, a HEPA filtering medium including glass fiber is installed inside the frame body.
  • the average fiber diameter of glass fiber was about 0.5 ⁇ m.
  • Example 7 the processing and evaluation were made in the same manner as Example 5 except that a HEPA filtering medium laminated with a pre-collecting layer including polypropylene, which was obtained by a melt blown method, at the upstream side of a HEPA filter made of common PTFE (average fiber diameter of about 70 nm) is used.
  • the average fiber diameter of the pre-collecting layer was about 1.1 ⁇ m.
  • Example 5 and Comparative Examples 6 and 7 are presented in Table 3.
  • Example 5 Comparative Example 6 Comparative Example 7 Filtering medium Filtering medium of Example 1 Glass HEPA PP melt blown + PTFE membrane HEPA Pressure loss (Pa) 175 350 250 Filter life span (g/m 2 ) 10 10 10 Power consumption amount (kwh) 1800-2100 3250-4100 2500-2950 Energy saving effect (1000 Yen/year) 20-28 - 10-16
  • the filtering medium produced according to the present invention has lower pressure loss compared to a glass filtering medium and also has significantly improved dust holding capacity (that is, filter life span) which has been remained as a problem of PTFE filtering medium of a related art, showing almost the same capacity as the glass filtering medium. Further, a filter with long life span can be manufactured due to low pressure loss. As a result, a significant energy saving can be achieved compared to a filtering medium of a related art (Comparative Examples 6 and 7)
  • the hydrocarbon oil (manufactured by Idemitsu Kosan Co., Ltd., "IP SOLVENT 2028") was added at 20°C in an amount of 32 parts by weight per 100 parts by weight of the mixture followed by mixing.
  • the obtained mixture was extruded using a paste extruder to obtain a molded product with a sheet shape.
  • a sheet die formed with a rectangular extrusion outlet having width direction length of 2 mm xlength direction length of 150 mm was added.
  • the molded product with a sheet shape was molded into a film shape using a calendar roll heated to 70°C to obtain a PTFE film.
  • the film was passed through a heat wave drying furnace at 250°C to remove the hydrocarbon oil by evaporation, thus obtaining an unsintered PTFE film with band shape having average thickness of 300 ⁇ m and average width of 150 mm.
  • the unsintered PTFE film was drawn in the length direction at drawing ratio of 5 times and drawing speed of 40%/second.
  • the drawing temperature was 300°C.
  • the drawn but unsintered film was drawn in the width direction at drawing ratio of 13.5 times and drawing speed of 162%/second by using a tenter capable of continuous clipping followed by thermal fixing. At that time, the drawing temperature was 290°C and the temperature for thermal fixing was 390°C. Accordingly, a porous membrane (filling ratio of 4.0%, average fiber diameter of 0.105 ⁇ m, and thickness of 55.0 ⁇ m) was obtained.
  • Example 11 The processing and evaluation were made in the same manner as Example 11 except that the drawing is performed by using a tenter with the drawing ratio of 15 times in the width direction and the drawing speed of 180%/second.
  • Example 11 The processing and evaluation were made in the same manner as Example 11 except that the unsintered film is drawn at drawing ratio of 7.5 times in the length direction and drawing speed of 125%/second and the drawing is performed by using a tenter with the drawing ratio of 15 times in the width direction and the drawing speed of 180%/second.
  • the drawing was performed in the same manner as the unsintered film of Example 11 while overlapping two layers of the unsintered PTFE film produced and performing the drawing with the drawing ratio of 7.5 times in the length direction and the drawing speed of 125%/second.
  • the drawing temperature was 300°C.
  • the drawn but unsintered film was drawn in the width direction at drawing ratio of 15 times and drawing speed of 180%/second by using a tenter capable of continuous clipping followed by thermal fixing. At that time, the drawing temperature was 290°C and the temperature for thermal fixing was 390°C.
  • Example 11 Thereafter, by attaching the air permeable support used in Example 11 to both sides (outer layer sides) of the obtained porous membrane with two layers by thermal fixing using a lamination apparatus, the filtering medium with four layer structure as illustrated in Fig. 6 was obtained.
  • the obtained filtering medium was evaluated in the same manner as Example 11.
  • Example 11 The processing and evaluation were made in the same manner as Example 11 except that the drawing is performed by using a tenter with the drawing ratio of 28 times in the width direction and the drawing speed of 347%/second.
  • Example 11 The processing and evaluation were made in the same manner as Example 11 except that PTFE aqueous dispersion (PTFE-A) with SSG of 2.160 is used but the hot melt processable component that is not fibrillated and the non-hot melt processable component that is not fibrillated are not used, 32 parts by weight of liquid lubricant for extrusion is added followed by mixing, and the drawing is performed by using a tenter with the drawing ratio of 24 times in the width direction and the drawing speed of 298%/second.
  • PTFE-A aqueous dispersion
  • SSG SSG of 2.160
  • 32 parts by weight of liquid lubricant for extrusion is added followed by mixing
  • the drawing is performed by using a tenter with the drawing ratio of 24 times in the width direction and the drawing speed of 298%/second.
  • Example 11 The processing and evaluation were made in the same manner as Example 11 except that the hot melt processable component that is not fibrillated is not used, the mixing ratio between PTFE that can be fibrillated and the non-hot melt processable component that is not fibrillated is changed (that is, 70% by weight (in terms of polymer) of PTFE aqueous dispersion (PTFE-A) with SSG of 2.160 and 30% by weight (in terms of polymer) of low molecular weight PTFE aqueous dispersion (PTFE-B) with melt viscosity of 20000 Pa ⁇ s which is measured by a flow tester method at 380°C), and the drawing is performed by using a tenter with the drawing ratio of 20 times in the width direction and the drawing speed of 248%/second.
  • PTFE-A PTFE aqueous dispersion
  • PTFE-B low molecular weight PTFE aqueous dispersion
  • melt viscosity 20000 Pa ⁇ s which is measured by a flow tester method at
  • Example 11 The processing and evaluation were made in the same manner as Example 11 except that the non-hot melt processable component that is not fibrillated is not used, the mixing ratio between PTFE that can be fibrillated and the hot melt processable component that is not fibrillated is changed (that is, 90% by weight (in terms of polymer) of PTFE aqueous dispersion (PTFE-A) with SSG of 2.160 and 10% by weight (in terms of polymer) of aqueous dispersion of FEP with melting temperature of 215°C), and the drawing is performed by using a tenter with the drawing ratio of 20 times in the width direction and the drawing speed of 248%/second.
  • PTFE-A PTFE aqueous dispersion
  • SSG 0.160
  • 10% by weight (in terms of polymer) of aqueous dispersion of FEP with melting temperature of 215°C aqueous dispersion of FEP with melting temperature of 215°C
  • the dust holding capacity (PAO) of the filtering medium was 25.0 g/m 2 and the dust holding capacity (NaCl) was 5.3 g/m 2 . Meanwhile, the raw material component, conditions for producing, and porous membrane are omitted for Reference example 1 of Table 4.
  • the filling ratio of porous membrane was calculated according to the following equation.
  • Filling ratio % Specific gravity of porous membrane / Specific gravity of raw material ⁇ 100
  • Specific gravity of porous membrane Weight of porous membrane / Membrane thickness of porous membrane ⁇ Area of porous membrane
  • the specific gravity of the raw material is represented by a value which is obtained by dividing the sum of the product of gravity of each component with weight ratio of each component by the sum of the weight ratio.
  • the surface of the porous membrane was photographed by scanning electron microscopy (SEM). It was then obtained by measuring fiber diameter for 10 or more areas from the obtained photograph and calculating the average value of the measured values.
  • the membrane pressure of the five overlapped porous membranes as a whole was measured.
  • the resulting value was divided by 5 to give the membrane thickness of one porous membrane.
  • the membrane thickness indicates the membrane thickness relative to one porous membrane as a whole (that is, average membrane thickness).
  • a test sample of the filtering medium was set in a filter holder with diameter of 100 mm.
  • the inlet side was pressurized using a compressor and the air flow amount was set at 5.3 cm/second by using a flow meter.
  • the pressure loss at that time was measured by using a manometer.
  • the collection efficiency was calculated in the same manner as the calculating the collection efficiency for NaCl particles with particle diameter of 0.3 ⁇ m except that the NaCl particles with particle diameter of 0.1 ⁇ m are used instead of the NaCl particles with particle diameter of 0.3 ⁇ m.
  • the PF value was calculated in the same manner as the obtainment of the PF value (NaCl particles with particle diameter of 0.3 ⁇ m) except that the collection efficiency (NaCl particles with particle diameter of 0.1 ⁇ m) is inserted of the collection efficiency (NaCl particles with particle diameter of 0.3 ⁇ m).
  • the initial filter pressure loss is about 250 Pa or less for a HEPA unit and, with regard to the filter exchange time, the time point at which the loss is more than two times the initial filter pressure loss is generally recommended. Further, the initial pressure loss of a glass filtering medium for a standard HEPA is about 250 to 300 Pa. For such reasons, the time point at which the pressure loss is increased to 250 Pa was taken as the end point of the above test for evaluating the dust holding capacity of the filtering medium.
  • Evaluation was made based on the pressure loss build-up test at the time of passage of NaCl particles. That is, pressure loss when air including NaCl particles was continuously passed at a flow rate of 5.3 cm/sec through a sample filtering medium with an effective filtration area of 50 cm 2 was measured over time with a differential pressure gauge (U-tube manometer), and when pressure loss increased to 250 Pa, the dust holding capacity (g/m 2 ), which is the weight, per unit area of the filtering medium, of the NaCl particles held in the filtering medium, was obtained.
  • the NaCl particles NaCl particles (with a count median diameter of 0.05 ⁇ m) generated with a Laskin nozzle were used, and the concentration of the NaCl particles was about 1,000,000 to 3,000,000/cm 3 .
  • the pressure loss was measured by using a filter holder with diameter of 100 mm.
  • the pressure loss measurement was performed by continuous measurement of plural areas in lattice shape by using a measurement apparatus provided with at least five filter holders in the width direction of the filtering medium while moving the filtering medium in the length direction.
  • the standard deviation was obtained from the pressure loss distribution which includes the measured pressure losses. Further, by dividing the obtained standard deviation with the average pressure loss in every measured area, the coefficient of variation (%) was obtained.
  • the "raw material” means the raw material of the porous membrane
  • the "co-coagulated product” means a material for molding including the polytetrafluoroethylene that can be fibrillated, the non-hot melt processable component that is not fibrillated, and the hot melt processable component with a melting point of lower than 320°C that is not fibrillated that are described above
  • the "homo PTFE” indicates the homo PTFE for producing a porous PTFE membrane of a related art.
  • the number indicated in the column “layer structure” means the number of layers. When the number of layer is 5 and there is only one number in the column “length drawing ratio”, it means that two pieces of the porous membrane having the same drawing ratio are used.
  • Measurement limit means that it is more than the upper limit which can be measured.
  • Example 11 Example 12
  • Example 13 Example 14
  • Raw material component Component A (% by weight) 66.5 66.5 66.5 66.5
  • Component B (% by weight) 28.5 28.5 28.5
  • Component C (% by weight) 5 5 5 5 5
  • Average fiber diameter ( ⁇ m) 0.105 0.100 0.108 0.110 Thickness of one layer of porous membrane ( ⁇ m) 55 50 52 45 Thickness of porous membrane in total ( ⁇ m) 110 100 104 90 Filtering medium Layer structure 5 5 5 4 Pressure loss (Pa) 155 152 148 150 Collection efficiency(%) 0.3 ⁇ m,
  • the drawing ratio in width direction was high, that is, more than 25 times, and the drawing speed was fast in Comparative Examples 11, and thus the porous membrane was excessively thin and the fiber diameter was small so that the dust holding capacity with PAO was low.
  • the dust holding capacity of the filtering medium is lowered due to compression of the membrane during a post step as caused by the absence of the hot melt processable component.
  • the dust holding capacity of the filtering medium is lowered due to insufficient suppression of an occurrence of thin fiber as caused by the absence of the hot melt processable component that is not fibrillated.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Filtering Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Filtering Of Dispersed Particles In Gases (AREA)
  • Laminated Bodies (AREA)

Claims (4)

  1. Gemischtes Pulver mit Polytetrafluorethylen als eine Hauptkomponente, welches folgendes umfasst:
    (i) ein Polytetrafluorethylen mit hohem Molekulargewicht, das fibrilliert werden kann,
    (ii) ein Polytetrafluorethylen mit niedrigem Molekulargewicht, ein wärmehärtbares Harz oder einen anorganischen Füllstoff als eine nicht-heißschmelz-verarbeitbare Komponente, die nicht fibrilliert ist, und
    (iii) ein heißschmelz-verarbeitbares Fluorpolymer, Silicon, Polystyrol, Polyethylenterephthalat, Polyester, Polyamid, Acrylharz, Urethanharz oder eine Mischung davon als eine heißschmelz-verarbeitbare Komponente mit einem Schmelzpunkt von niedriger als 320 °C, die nicht fibrilliert ist,
    wobei der Gehalt von (ii) der nicht-heißschmelz-verarbeitbaren Komponente 20 bis 40 Gewichts-% des Gesamten beträgt, und
    wobei (iii) die heißschmelz-verarbeitbare Komponente, die nicht fibrilliert ist, zu gleich oder mehr als 0,1 Gewichts-% aber weniger als 20 Gewichts-% des Gesamten enthalten ist.
  2. Material zum Formen mit Polytetrafluorethylen als eine Hauptkomponente, welches folgendes umfasst:
    (i) ein Polytetrafluorethylen mit hohem Molekulargewicht, das fibrilliert werden kann,
    (ii) ein Polytetrafluorethylen mit niedrigem Molekulargewicht, ein wärmehärtbares Harz oder einen anorganischen Füllstoff als eine nicht-heißschmelz-verarbeitbare Komponente, die nicht fibrilliert ist, und
    (iii) ein heißschmelz-verarbeitbares Fluorpolymer, Silicon, Polystyrol, Polyethylenterephthalat, Polyester, Polyamid, Acrylharz, Urethanharz oder eine Mischung davon als eine heißschmelz-verarbeitbare Komponente mit einem Schmelzpunkt von niedriger als 320 °C, die nicht fibrillier ist, und
    (iv) eine Verarbeitungshilfe,
    wobei der Gehalt von (ii) der nicht-heißschmelz-verarbeitbaren Komponente 20 bis 40 Gewichts-% des Gesamten von (i) dem Polytetrafluorethylen mit hohem Molekulargewicht, (ii) der nicht-heißschmelz-verarbeitbaren Komponente und (iii) der heißschmelz-verarbeitbaren Komponente beträgt, und
    wobei die (iii) heißschmelz-verarbeitbare Komponente, die nicht fibrilliert ist, zu gleich oder mehr als 0,1 Gewichts-% aber weniger als 20 Gewichts-% des Gesamten von (i) dem Polytetrafluorethylen mit hohem Molekulargewicht, (ii) der nicht-heißschmelz-verarbeitbaren Komponente und (iii) der heißschmelz-verarbeitbaren Komponente enthalten ist.
  3. Verwendung des Materials gemäß Anspruch 2 zum Formen einer porösen Membran, die für ein Filtermedium für einen Filter zum Erfassen von Feinpartikeln in Flüssigkeit verwendet wird.
  4. Poröse Membran, die das Material gemäß mindestens einem der Ansprüche 1 oder 2 umfasst.
EP16172614.6A 2012-04-20 2013-04-19 Zusammensetzung mit ptfe als hauptkomponente, gemischtes pulver und material zum formen Active EP3118256B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2012096510 2012-04-20
JP2013075534 2013-03-31
PCT/JP2013/061685 WO2013157647A1 (ja) 2012-04-20 2013-04-19 Ｐｔｆｅを主成分とする組成物、混合粉末、成形用材料、及びフィルタ用濾材、エアフィルタユニット、並びに多孔膜の製造方法
EP13778043.3A EP2840115B1 (de) 2012-04-20 2013-04-19 Zusammensetzung weitgehend auf basis von ptfe, mischpulver, formmasse, filtermedium für filter, luftfiltereinheit und verfahren zur herstellung einer porösen membran

Related Parent Applications (2)

Application Number Title Priority Date Filing Date
EP13778043.3A Division EP2840115B1 (de) 2012-04-20 2013-04-19 Zusammensetzung weitgehend auf basis von ptfe, mischpulver, formmasse, filtermedium für filter, luftfiltereinheit und verfahren zur herstellung einer porösen membran
EP13778043.3A Division-Into EP2840115B1 (de) 2012-04-20 2013-04-19 Zusammensetzung weitgehend auf basis von ptfe, mischpulver, formmasse, filtermedium für filter, luftfiltereinheit und verfahren zur herstellung einer porösen membran

Publications (2)

Publication Number Publication Date
EP3118256A1 EP3118256A1 (de) 2017-01-18
EP3118256B1 true EP3118256B1 (de) 2020-07-15

Family

ID=49383593

Family Applications (2)

Application Number Title Priority Date Filing Date
EP13778043.3A Active EP2840115B1 (de) 2012-04-20 2013-04-19 Zusammensetzung weitgehend auf basis von ptfe, mischpulver, formmasse, filtermedium für filter, luftfiltereinheit und verfahren zur herstellung einer porösen membran
EP16172614.6A Active EP3118256B1 (de) 2012-04-20 2013-04-19 Zusammensetzung mit ptfe als hauptkomponente, gemischtes pulver und material zum formen

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP13778043.3A Active EP2840115B1 (de) 2012-04-20 2013-04-19 Zusammensetzung weitgehend auf basis von ptfe, mischpulver, formmasse, filtermedium für filter, luftfiltereinheit und verfahren zur herstellung einer porösen membran

Country Status (6)

Country Link
US (2) US9707504B2 (de)
EP (2) EP2840115B1 (de)
JP (3) JP5862766B2 (de)
CN (3) CN104245827B (de)
TW (2) TWI543811B (de)
WO (1) WO2013157647A1 (de)

Families Citing this family (65)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9361137B2 (en) 2006-03-10 2016-06-07 International Business Machines Corporation Managing application parameters based on parameter types
US8455242B2 (en) 2010-02-22 2013-06-04 Hyclone Laboratories, Inc. Mixing system with condenser
US9295931B2 (en) * 2011-07-05 2016-03-29 Nitto Denko Corporation Porous polytetrafluoroethylene membrane and air filter medium
PL2750725T3 (pl) * 2011-09-01 2021-05-17 Anatoli D. Dosta Pojedynczy implant, implant naczyniowy i implant tkankowy wykonany z porowanej trójwymiarowej struktury politetrafluoroetylenowej
JP5862766B2 (ja) * 2012-04-20 2016-02-16 ダイキン工業株式会社 Ｐｔｆｅを主成分とするフィルタ用濾材、エアフィルタユニット、並びに多孔膜の製造方法
US10245545B2 (en) * 2013-10-23 2019-04-02 Daikin Industries, Ltd. Embossed air filter filtration medium, filter pack, air filter unit, and method for manufacturing filtration medium for embossed air filter
CN105849958B (zh) 2013-11-29 2019-10-29 旭化成株式会社 高分子电解质膜
US10688448B2 (en) 2013-11-29 2020-06-23 Daikin Industries, Ltd. Porous body, polymer electrolyte membrane, filter material for filter, and filter unit
CN105793336B (zh) * 2013-11-29 2019-12-24 大金工业株式会社 双向拉伸多孔质膜
TW201533125A (zh) 2013-11-29 2015-09-01 Daikin Ind Ltd 改性聚四氟乙烯細粉及單軸拉伸多孔質體
KR20160091386A (ko) 2013-11-29 2016-08-02 아사히 가세이 가부시키가이샤 고분자 전해질막
US10688429B2 (en) 2014-03-21 2020-06-23 Life Technologies Corporation Gas filter systems for fluid processing systems
JP5835389B2 (ja) * 2014-03-26 2015-12-24 ダイキン工業株式会社 エアフィルタ用濾材、フィルタパック、エアフィルタユニット、およびエアフィルタ用濾材の製造方法
US9320999B2 (en) * 2014-05-07 2016-04-26 Ned Abell Method and device for removing airborne pollutants
US20160016124A1 (en) * 2014-07-21 2016-01-21 W.L. Gore & Associates, Inc. Fluoropolymer Article for Mycoplasma Filtration
US20160016126A1 (en) * 2014-07-21 2016-01-21 W. L. Gore & Associates, Inc Fluoropolymer Article For Bacterial Filtration
WO2016021239A1 (ja) * 2014-08-07 2016-02-11 日本バイリーン株式会社 通気性シート
JP6409488B2 (ja) * 2014-10-15 2018-10-24 住友電気工業株式会社 多孔質積層体
US11819792B2 (en) * 2014-11-14 2023-11-21 Columbus Industries, Inc. Bidirectional airflow filter
CN104497454B (zh) * 2014-12-01 2016-07-27 湖州绿净环保科技有限公司 一种空气过滤用聚四氟乙烯薄膜
CN104448637B (zh) * 2014-12-01 2016-08-17 湖州绿净环保科技有限公司 一种空气过滤用聚四氟乙烯薄膜的制备方法
CN104436858A (zh) * 2014-12-17 2015-03-25 上海海凡滤材有限公司 一种三层复合滤布及其制造方法
WO2016104589A1 (ja) * 2014-12-26 2016-06-30 ダイキン工業株式会社 エアフィルタ用濾材、フィルタパック、エアフィルタユニット、およびエアフィルタ用濾材の製造方法
JP6115596B2 (ja) * 2014-12-26 2017-04-19 ダイキン工業株式会社 エアフィルタ用濾材、フィルタパック、エアフィルタユニット、およびエアフィルタ用濾材の製造方法
CN107848180B (zh) * 2015-08-04 2019-10-18 Ａｇｃ株式会社 氟树脂膜的制造方法
US11326034B2 (en) * 2015-09-07 2022-05-10 Sumitomo Electric Fine Polymer Method for manufacturing polytetrafluoroethylene formed product, and polytetrafluoroethylene formed product
CN105153607A (zh) * 2015-09-24 2015-12-16 傅兴琴 一种绝缘电缆护套材料的制备方法
CN105749981B (zh) * 2016-04-01 2018-04-03 河海大学 一种碳纳米管/氧化锌ptfe膜及其制备方法
CN106310969A (zh) * 2016-09-23 2017-01-11 广州仕瀚环保科技有限公司 活性碳膜丝
CN106237876A (zh) * 2016-09-26 2016-12-21 江苏久朗高科技股份有限公司 一种多功能复合膜材料及其生产工艺
JP6861493B2 (ja) * 2016-09-30 2021-04-21 日東電工株式会社 エアフィルタ濾材、エアフィルタパック及びエアフィルタユニット
JP6920042B2 (ja) * 2016-09-30 2021-08-18 日東電工株式会社 エアフィルタ濾材、エアフィルタパック及びエアフィルタユニット
CN106582112B (zh) * 2016-11-04 2019-04-16 中材科技股份有限公司 一种半干法脱硫烟气净化滤料及其制备方法
JP7208014B2 (ja) 2016-12-19 2023-01-18 日東電工株式会社 ポリテトラフルオロエチレン多孔質膜とこれを用いた防水通気膜及び防水通気部材
JPWO2018116513A1 (ja) * 2016-12-22 2019-10-24 住友電工ファインポリマー株式会社 多孔質材料、ガスセンサ及び多孔質材料の製造方法
AU2018205453B2 (en) * 2017-01-06 2021-02-04 W. L. Gore & Associates Gmbh Hood including particle barrier
CN106861315B (zh) * 2017-02-25 2022-11-18 秦皇岛同力达环保能源股份有限公司 一种高温膜除尘组件及高温膜除尘器
JP6584614B2 (ja) * 2017-09-22 2019-10-02 日東電工株式会社 エアフィルタ濾材、フィルタプリーツパックおよびエアフィルタユニット
JP7356971B2 (ja) * 2018-06-01 2023-10-05 日東電工株式会社 フィルタ濾材とこれを備えるフィルタユニット
KR101998031B1 (ko) * 2018-06-29 2019-07-08 닛토덴코 가부시키가이샤 에어 필터 유닛 및 공조기
CN110712348B (zh) * 2018-07-12 2022-01-11 大金工业株式会社 成型品的制造方法和成型品
JP6816746B2 (ja) * 2018-07-20 2021-01-20 ダイキン工業株式会社 エアフィルタ濾材、フィルタパック、およびエアフィルタユニット
JP2020043920A (ja) 2018-09-14 2020-03-26 日本無機株式会社 空気清浄装置、及び空気清浄方法
US20220040614A1 (en) * 2018-09-28 2022-02-10 Daikin Industries, Ltd. Air filter medium, filter pack, air filter unit, and method for producing the same
EP3860746A1 (de) * 2018-10-04 2021-08-11 W.L. Gore & Associates Inc. Ungesinterte, expandierte polytetrafluorethylen-verbundmembranen mit formbeständigkeit
CN109316828B (zh) * 2018-10-17 2019-07-05 江苏氟莱尔环保科技有限公司 一种耐高温滤布材料
CN109529639B (zh) * 2018-11-05 2021-08-17 宁波水艺膜科技发展有限公司 高粘结强度聚四氟乙烯中空纤维膜的制备方法
CN113227216A (zh) * 2018-12-25 2021-08-06 Ａｇｃ株式会社 粉末分散液、层叠体的制造方法、聚合物膜的制造方法和被覆织布的制造方法
JP6661098B1 (ja) * 2019-01-28 2020-03-11 有限会社ヤマカツラボ 積層ポリテトラフルオロエチレン多孔膜及びその製法
CN109655434B (zh) * 2019-02-22 2024-01-26 东北大学 一种多参数测量的光纤lmr传感器
US20220282413A1 (en) 2019-08-30 2022-09-08 Daicel Corporation Method for producing fiber articles
EP4023803A4 (de) 2019-08-30 2023-09-06 Daicel Corporation Faserartikel
US20230025947A1 (en) * 2019-12-05 2023-01-26 Nitto Denko Corporation Stretched porous polytetrafluoroethylene membrane, air-permeable medium using the same, and filter member using the same
CN111111474B (zh) * 2019-12-23 2022-08-09 爱舍环境科技(成都)有限公司 空气过滤用介质
CN111234269B (zh) * 2020-03-18 2022-05-06 山东东岳高分子材料有限公司 一种填充聚四氟乙烯分散树脂的制备方法
CN111991920A (zh) * 2020-07-02 2020-11-27 南京玻璃纤维研究设计院有限公司 一种过滤材料及其制备方法
US10989304B1 (en) * 2020-07-27 2021-04-27 Teadit N.A., Inc. Compression packing
US11660566B2 (en) 2020-08-05 2023-05-30 H24Us Corp. Hydrogen purification using molecular dynamics
US11400423B2 (en) * 2020-08-05 2022-08-02 H24Us Corp Hydrogen purification using molecular dynamics
CN112221277B (zh) * 2020-10-30 2024-06-18 西华大学 一种空气过滤器
CN112745608B (zh) * 2020-12-29 2023-07-28 施柏德（厦门）科技有限公司 一种均匀性优异的ptfe复合材料及其制作工艺和应用
JP7181480B2 (ja) * 2021-02-04 2022-12-01 ダイキン工業株式会社 エアフィルタ濾材、エアフィルタ濾材の製造方法、マスク用濾材、および、プリーツ状マスク用濾材
JP7219412B2 (ja) * 2021-06-04 2023-02-08 ダイキン工業株式会社 エアフィルタ濾材、プリーツ状濾材、エアフィルタユニット、マスク用濾材、および、エアフィルタ濾材の再生方法
USD1027682S1 (en) 2021-09-30 2024-05-21 Carrier Corporation Refrigerant detection sensor housing
CN116173621B (zh) * 2023-02-16 2023-09-29 江苏奥凯环境技术有限公司 一种用于超低排放的芳纶过滤材料及其生产工艺

Family Cites Families (77)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5225419B2 (de) 1972-01-20 1977-07-07 Japan Atomic Energy Res Inst
US4129470A (en) * 1974-10-17 1978-12-12 Homsy Charles A Method of preparing a porous implantable material from polytetrafluoroethylene and carbon fibers
JPS5360979A (en) 1976-11-11 1978-05-31 Daikin Ind Ltd Polytetrafluoroethylene fine powder and its preparation
JPS5618624A (en) * 1979-07-24 1981-02-21 Daikin Ind Ltd Production of filled polytetrafluoroethylene fine powder
JPS5839443B2 (ja) 1980-05-31 1983-08-30 ダイキン工業株式会社 ポリテトラフルオロエチレンフアインパウダ−の製造方法
JPS6042446A (ja) 1983-04-28 1985-03-06 イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− 分散液で製造された変性ポリテトラフルオルエチレン組成物
US4555543A (en) * 1984-04-13 1985-11-26 Chemical Fabrics Corporation Fluoropolymer coating and casting compositions and films derived therefrom
US4576869A (en) 1984-06-18 1986-03-18 E. I. Du Pont De Nemours And Company Tetrafluoroethylene fine powder and preparation thereof
JPS61162503A (ja) 1985-01-10 1986-07-23 Central Glass Co Ltd 含フツ素樹脂の低分子量物の製造方法
US4654406A (en) 1985-09-09 1987-03-31 E. I. Du Pont De Nemours And Company Preparation of tetrafluoroethylene fine powder
US4748217A (en) 1986-01-27 1988-05-31 E. I. Du Pont De Nemours And Company Preparation of tetrafluoroethylene fine powder
DE3787590T2 (de) 1986-07-21 1994-03-10 Daikin Ind Ltd Polytetrafluoräthylenhaltige Beschichtungsmasse und ihre Verwendung.
JPS63168448A (ja) * 1987-01-05 1988-07-12 Daikin Ind Ltd ポリテトラフルオロエチレン被覆用組成物
GB8628291D0 (en) 1986-11-26 1986-12-31 Ici Plc Tetrafluoroethylene polymers
JP2551005B2 (ja) 1987-06-24 1996-11-06 ダイキン工業株式会社 変性ポリテトラフルオロエチレンフアインパウダ−及びその製造方法
US4908410A (en) 1989-01-27 1990-03-13 E. I. Du Pont De Nemours And Company Modified polytetrafluoroethylene fine powder and preparation thereof
JP2814574B2 (ja) * 1989-06-15 1998-10-22 住友電気工業株式会社 ポリテトラフルオロエチレン多孔質体およびその製造方法
US5071610A (en) * 1990-02-23 1991-12-10 Minnesota Mining And Manufacturing Company Method of making a controlled pore composite polytetrafluoroethylene
JP3163484B2 (ja) 1990-09-29 2001-05-08 アンリツ株式会社 波形整形回路およびディジタル信号解析装置
GB9106481D0 (en) * 1991-03-27 1991-05-15 Pall Corp Filters and filter units
US5230952A (en) * 1991-06-17 1993-07-27 Coltec Industries Inc. Sintered composite friction material comprising fluorocarbon resin
DE4331971A1 (de) 1993-09-21 1995-03-23 Hoechst Ag Polytetrafluorethylen-Mikropulver, ihre Herstellung und Verwendung
US5527353A (en) * 1993-12-02 1996-06-18 Meadox Medicals, Inc. Implantable tubular prosthesis
US5753358A (en) * 1994-08-25 1998-05-19 W. L. Gore & Associates, Inc. Adhisive-filler polymer film composite
CN1145600A (zh) 1994-09-02 1997-03-19 W·L·戈尔及同仁股份有限公司 多孔聚四氟乙烯组合物
JPH0878252A (ja) 1994-09-08 1996-03-22 Otsuka Sci Kk 共振型空心変圧器
US6929985B2 (en) * 1995-07-27 2005-08-16 Taisei Corporation Air filter, method of manufacturing air filter, local facility, clean room, treating agent, and method of manufacturing filter medium
US5814405A (en) 1995-08-04 1998-09-29 W. L. Gore & Associates, Inc. Strong, air permeable membranes of polytetrafluoroethylene
JP3931382B2 (ja) 1996-09-18 2007-06-13 ダイキン工業株式会社 ポリテトラフルオロエチレン粉末及びその製造方法
TW406101B (en) * 1997-01-20 2000-09-21 Daikin Inpustries Ltd Filter medium and air filter unit using the same
US6239223B1 (en) * 1997-09-05 2001-05-29 Chemfab Corporation Fluoropolymeric composition
JP3669172B2 (ja) 1997-12-25 2005-07-06 旭硝子株式会社 テトラフルオロエチレン系共重合体、その製造方法およびその用途
JP3613024B2 (ja) 1997-12-26 2005-01-26 旭硝子株式会社 延伸用テトラフルオロエチレン系共重合体とその用途
JP2003520863A (ja) * 1998-08-06 2003-07-08 オムリドン テクノロジーズ エルエルシー 溶融加工性ポリ（テトラフルオロエチレン）
JP2000143922A (ja) * 1998-11-06 2000-05-26 Asahi Glass Co Ltd ポリテトラフルオロエチレン組成物
US6177533B1 (en) 1998-11-13 2001-01-23 E. I. Du Pont De Nemours And Company Polytetrafluoroethylene resin
US6342294B1 (en) 1999-08-12 2002-01-29 Bruce G. Ruefer Composite PTFE article and method of manufacture
US6521284B1 (en) * 1999-11-03 2003-02-18 Scimed Life Systems, Inc. Process for impregnating a porous material with a cross-linkable composition
JP3552685B2 (ja) 2000-10-30 2004-08-11 旭硝子株式会社 強度に優れるテトラフルオロエチレン重合体
US7560006B2 (en) * 2001-06-11 2009-07-14 Boston Scientific Scimed, Inc. Pressure lamination method for forming composite ePTFE/textile and ePTFE/stent/textile prostheses
US6827737B2 (en) * 2001-09-25 2004-12-07 Scimed Life Systems, Inc. EPTFE covering for endovascular prostheses and method of manufacture
US6541589B1 (en) 2001-10-15 2003-04-01 Gore Enterprise Holdings, Inc. Tetrafluoroethylene copolymer
FR2838631B1 (fr) * 2002-04-23 2004-12-24 Engeneering And Technological Procede de realisation d'une prothese de valve cardiaque aortique ou mitrale et prothese de valve cardiaque aortique ou mitrale ainsi obtenue
US6737158B1 (en) * 2002-10-30 2004-05-18 Gore Enterprise Holdings, Inc. Porous polymeric membrane toughened composites
US7176265B2 (en) 2002-11-22 2007-02-13 E. I. Du Pont De Nemours And Company Directly polymerized low molecular weight granular polytetrafluoroethylene
US7008465B2 (en) * 2003-06-19 2006-03-07 Donaldson Company, Inc. Cleanable high efficiency filter media structure and applications for use
WO2005019336A1 (ja) * 2003-08-25 2005-03-03 Daikin Industries, Ltd. 成形体及びその製造方法、高周波信号伝送用製品並びに高周波伝送ケーブル
JP4951970B2 (ja) 2003-12-22 2012-06-13 ダイキン工業株式会社 非溶融加工性ポリテトラフルオロエチレン及びそのファインパウダー
JP4797347B2 (ja) 2004-08-25 2011-10-19 旭硝子株式会社 低分子量ポリテトラフルオロエチレン水性分散液の製造方法
EP1791496B1 (de) * 2004-08-31 2019-07-31 C.R. Bard, Inc. Selbstschliessendes ptfe-implantat mit knickbeständigkeit
JP4533115B2 (ja) 2004-12-03 2010-09-01 三井・デュポンフロロケミカル株式会社 フッ素樹脂成形方法及びフッ素樹脂成形品
US7531611B2 (en) 2005-07-05 2009-05-12 Gore Enterprise Holdings, Inc. Copolymers of tetrafluoroethylene
CN100558753C (zh) 2005-10-17 2009-11-11 旭硝子株式会社 聚四氟乙烯水性乳化液、由其制得的聚四氟乙烯细粉和多孔体
WO2007061927A2 (en) * 2005-11-18 2007-05-31 C. R. Bard, Inc. Vena cava filter with filament
WO2007119829A1 (ja) 2006-04-13 2007-10-25 Daikin Industries, Ltd. テトラフルオロエチレン重合体及びその水性分散液
US8147583B2 (en) * 2007-06-08 2012-04-03 Gore Enterprise Holdings, Inc. Multiple layer filter media
JP5532532B2 (ja) 2007-06-25 2014-06-25 ダイキン工業株式会社 低分子量ポリテトラフルオロエチレン水性分散液及びその製造方法
JP5257360B2 (ja) 2007-06-28 2013-08-07 ダイキン工業株式会社 ポリテトラフルオロエチレン水性分散液及びその製造方法
JP5338667B2 (ja) 2007-08-07 2013-11-13 ダイキン工業株式会社 低分子量ポリテトラフルオロエチレン水性分散液、低分子量ポリテトラフルオロエチレン粉末及び低分子量ポリテトラフルオロエチレンの製造方法
US7812081B2 (en) * 2008-02-26 2010-10-12 General Electric Company Methods of making a mixture for a PTFE membrane with inorganic materials, and compositions related thereto
CA2737586C (en) * 2008-09-26 2016-11-08 Whitford Corporation Blended fluoropolymer compositions and coatings for flexible substrates
CN101543734B (zh) * 2008-11-21 2010-12-22 北京千叶宝莲科技有限公司 一种聚四氟乙烯纳米纤维膜及其制备方法
JP2010235667A (ja) 2009-03-30 2010-10-21 Daikin Ind Ltd 含フッ素ポリマーの製造方法
WO2010113950A1 (ja) 2009-03-30 2010-10-07 ダイキン工業株式会社 ポリテトラフルオロエチレン及びその製造方法
US8754176B2 (en) 2009-03-31 2014-06-17 Daikin Industries, Ltd. Low molecular weight polytetrafluoroethylene powder and preparation method therefor
ES2384910T3 (es) * 2009-04-02 2012-07-13 W.L. Gore & Associates Gmbh Casete de filtrado, dispositivo de filtrado y turbina de gas con dicho casete de filtrado
JP5668689B2 (ja) 2009-11-09 2015-02-12 旭硝子株式会社 ポリテトラフルオロエチレン水性乳化液及びその製造方法、該水性乳化液を用いて得られるポリテトラフルオロエチレン水性分散液、ポリテトラフルオロエチレンファインパウダー並びに延伸多孔体
JP2011177986A (ja) * 2010-02-26 2011-09-15 Daikin Industries Ltd シート、及び、巻物
JP5434753B2 (ja) 2010-03-31 2014-03-05 ダイキン工業株式会社 含フッ素重合体のオルガノゾル組成物
JP5012990B2 (ja) 2010-06-17 2012-08-29 ダイキン工業株式会社 多孔膜を備える濾材、その製造方法、フィルタパック、ならびにフィルタユニット
JP5533961B2 (ja) 2011-08-25 2014-06-25 ダイキン工業株式会社 ポリテトラフルオロエチレン水性分散液の製造方法
US20130108845A1 (en) * 2011-10-31 2013-05-02 YitHong Tee Oleophobic membrane structures including a porous polymeric coating
JP5862766B2 (ja) * 2012-04-20 2016-02-16 ダイキン工業株式会社 Ｐｔｆｅを主成分とするフィルタ用濾材、エアフィルタユニット、並びに多孔膜の製造方法
US20140142682A1 (en) * 2012-08-10 2014-05-22 W.L. Gore & Associates, Inc Implantable biocompatible tubular material
JP6426629B2 (ja) * 2013-02-11 2018-11-21 ダウ シリコーンズ コーポレーション アルコキシ官能性シロキサン反応性樹脂を含む湿気硬化性ホットメルトシリコーン接着剤組成物
US10245545B2 (en) * 2013-10-23 2019-04-02 Daikin Industries, Ltd. Embossed air filter filtration medium, filter pack, air filter unit, and method for manufacturing filtration medium for embossed air filter
PL3085428T3 (pl) * 2015-04-10 2020-10-05 Mann+Hummel Gmbh Element filtracyjny i układ filtra

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
TW201347839A (zh) 2013-12-01
JP6197835B2 (ja) 2017-09-20
JP6458817B2 (ja) 2019-01-30
JP5862766B2 (ja) 2016-02-16
EP2840115A1 (de) 2015-02-25
TWI639462B (zh) 2018-11-01
CN107088369A (zh) 2017-08-25
EP3118256A1 (de) 2017-01-18
TW201613686A (en) 2016-04-16
US10265661B2 (en) 2019-04-23
CN104245827A (zh) 2014-12-24
TWI543811B (zh) 2016-08-01
JP2016000817A (ja) 2016-01-07
CN105536384B (zh) 2017-09-19
EP2840115A4 (de) 2015-12-02
WO2013157647A1 (ja) 2013-10-24
JP2017122232A (ja) 2017-07-13
EP2840115B1 (de) 2018-06-06
US20180065094A1 (en) 2018-03-08
JPWO2013157647A1 (ja) 2015-12-21
CN105536384A (zh) 2016-05-04
CN104245827B (zh) 2019-09-06
US9707504B2 (en) 2017-07-18
US20150082757A1 (en) 2015-03-26

Similar Documents

Publication Publication Date Title
US10265661B2 (en) Mixed powder and material for molding having PTFE as main component, and drawn porous body
EP3124093B1 (de) Filtermedium für einen luftfilter, filterpaket, luftfiltereinheit und verfahren zur herstellung des filtermediums für einen luftfilter
EP3061512B1 (de) Geprägtes filtermedium für einen luftfilter, filterpaket, luftfiltereinheit und herstellungsverfahren für das geprägte filtermedium für einen luftfilter
US10406471B2 (en) Filter medium for air filter, filter pack, air filter unit, and method for producing filter medium for air filter
EP3427808A1 (de) Filtermedium für luftfilter, filterpaket, luftfiltereinheit und herstellungsverfahren für filtermedium für luftfilter
WO2018131573A1 (ja) エアフィルタ濾材
EP4289495A1 (de) Luftfilterfiltrationsmaterial, verfahren zur herstellung von luftfilterfiltrationsmaterial, filtrationsmaterial für masken und filtrationsmaterial für faltenmaske

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED

AC Divisional application: reference to earlier application

Ref document number: 2840115

Country of ref document: EP

Kind code of ref document: P

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: DAIKIN INDUSTRIES, LTD.

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20170718

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20191001

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTC Intention to grant announced (deleted)
INTG Intention to grant announced

Effective date: 20200226

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AC Divisional application: reference to earlier application

Ref document number: 2840115

Country of ref document: EP

Kind code of ref document: P

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602013070819

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1290995

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200815

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1290995

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200715

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200715

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201015

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200715

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201116

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200715

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200715

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200715

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201015

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201016

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200715

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200715

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200715

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200715

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201115

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602013070819

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200715

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200715

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200715

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200715

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200715

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200715

26N No opposition filed

Effective date: 20210416

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200715

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200715

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200715

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210419

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20210430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210430

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210430

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210419

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201115

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20130419

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200715

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230525

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20230228

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20240315

Year of fee payment: 12

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200715

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20240229

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20240313

Year of fee payment: 12